CN101668804B - Thermoplastic polycarbonate compositions - Google Patents

Abstract

A thermoplastic composition comprising from 30 to 89.5 wt. % of an aromatic polycarbonate, from 0.5 to 20 wt. % of an impact modifier, from 0 to 25 wt. % of an aromatic vinyl copolymer, from 6 to 35 wt. % of a mineral filler, and from 4 to 20 wt. % of a titanium dioxide, wherein the titanium dioxide is coated with silicone or siloxane, based on the total weight of the composition, has been found to exhibit improved mechanical properties and other characteristics and less degradation than filled thermoplastic compositions without the particular coated titanium dioxide. The composition optionally comprises an acid or acid salt. An article may be formed by molding, extruding, shaping or forming such a composition to form the article.

Description

Thermoplastic polycarbonate composition

Background technology

The present invention relates to comprise the thermoplastic compounds of aromatic polycarbonate, be specifically related to have filling (filled) thermoplastic polycarbonate composition that improves mechanical property.

Polycarbonate can be used for Application in manufacture goods and element widely, from the trolley part to the electron device.Because it is of many uses, particularly (for example in automobile is used) is of many uses in the field that replaces metal, thereby also need improve rigidity, reduction thermal expansivity when keeping excellent ductility and mobility.

A kind of currently known methods that improves the polycarbonate rigidity is to add mineral filler, for example talcum and mica.A problem that is accompanied by mineral-filled polycarbonate compositions and polycarbonate compositions blend is, and is mineral-filled, especially talcum and/or mica filled polycarbonate or polycarbonate Alloys can be degraded adding man-hour." degraded (degrade) " and " Degradation (degradation) " of polycarbonate used herein or polycarbonate Alloys are well known by persons skilled in the art, typically refer to molecular weight reduce and/or the change of machinery or physicals bad.

Thereby still need to reduce or control the degradation amount that the filled polymer material faces, and provide the filled-type material with the improvement mechanical property that is similar to unfilled polycarbonate and polycarbonate Alloys.

Summary of the invention

A kind of thermoplastic compounds comprises: by the gross weight of composition, the aromatic ethenyl copolymer of the aromatic polycarbonate of 30wt%～89.5wt%, the impact modifier of 0.5wt%～20wt%, 0～25wt%, the mineral filler of 6wt%～35wt% and the titanium dioxide of 4wt%～20wt%, wherein said titanium dioxide-coated has silicone or siloxanes.Described composition randomly comprises acid or acid salt (acid salt).Thermoplastic compounds of the present invention has improved mechanical property.

In a selective embodiment, a kind of thermoplastic compounds comprises: by the gross weight of composition, the vinyl aromatic copolymers of the aromatic polycarbonate resin of 30wt%～89.5wt%, the impact modifier of 0.5wt%～20wt%, 0～25wt%, the talcum of 6wt%～35wt% and the titanium dioxide of 4wt%～20wt%, wherein said titanium dioxide-coated has silicone or siloxanes.

By molding, extrude, shaping or moulding is this can making articles in order to the composition that forms goods.

In another embodiment, a kind of thermoplastic compounds is comprised of following material: by the gross weight of composition, and the aromatic polycarbonate resin of 50wt%～85wt%; The impact modifier of 1wt%～20wt%; The vinyl aromatic copolymers of 2wt%～25wt%; The talcum of 8wt%～25wt%; The acid of 0.01wt%～5wt% or acid salt; The titanium dioxide of 4wt%～20wt%, wherein said titanium dioxide-coated has silicone or siloxanes; The additive of 0.01wt%～7wt%, wherein said additive comprise filler, dripping inhibitor, thermo-stabilizer, photostabilizer, antioxidant, softening agent, static inhibitor, releasing agent, UV absorption agent, lubricant, pigment, dyestuff, tinting material or comprise the combination of two or more aforementioned substances.

The above and other feature is come illustration by following detailed description.

Embodiment

A kind of thermoplastic compounds comprises: by the gross weight of composition, the aromatic ethenyl copolymer of the aromatic polycarbonate of 30wt%～89.5wt%, the impact modifier of 0.5wt%～20wt%, 0～25wt%, the mineral filler of 6wt%～35wt% and the titanium dioxide of 4wt%～20wt%, wherein said titanium dioxide-coated has silicone or siloxanes.Described composition randomly comprises acid or acid salt.In some embodiments, said composition shows improved shock resistance and ductility, and excellent molecular weight retentivity (molecular weight retention)." excellent molecular weight retentivity " used herein means to be similar to or to there is no through the molecular weight of the polycarbonate that records after certain class processing the molecular weight that obviously is different from the front polycarbonate of processing.In other words, the molecular weight degradation effect is so so that its negative impact mechanical property in fact not.In one embodiment, the molecular weight retentivity is at least 80%, randomly at least 85%, and be at least 90% in some embodiments.In one embodiment, the molecular weight of described polycarbonate is 46000g/mol at least, 48000g/mol at least randomly, and optional 50000g/mol at least is based on the polystyrene calibration standard.Processing comprises for example compounding, molding, extrudes and other type processing means well known by persons skilled in the art.

In some embodiments, described acid or acid salt comprise phosphorous acid or acid salt.If exist, the amount of acid or acid salt can be 0.01wt%～5wt% or acid the weight ratio of filler is at least 0.0035: 1.

In some embodiments, impact modifier comprises ABS, MBS, body ABS (Bulk ABS), AES, ASA, MABS, polycarbonate-polysiloxane copolymer, and combination.In some embodiments, described aromatic ethenyl copolymer comprises SAN.

In an exemplary, described mineral filler is talcum.Can use any suitable talcum.In some embodiments, selecting size-grade distribution D50 is 3 microns or less meticulous talcum.

In a selective embodiment, thermoplastic compounds comprises: by the gross weight of composition, the aromatic polycarbonate resin of 30wt%～89.5wt%, the impact modifier of 0.5wt%～20wt%, the vinyl aromatic copolymers of 0～25wt%, the talcum of 6wt%～35wt%, and the titanium dioxide of 4wt%～20wt%, wherein said titanium dioxide-coated has silicone or siloxanes.

In another embodiment, thermoplastic compounds is comprised of following material: by the gross weight of composition, and the aromatic polycarbonate resin of 50wt%～85wt%; The impact modifier of 1wt%～20wt%; The vinyl aromatic copolymers of 2wt%～25wt%; The talcum of 8wt%～25wt%; The acid of 0.01wt%～5wt% or acid salt; The titanium dioxide of 4wt%～20wt%, wherein said titanium dioxide-coated has silicone or siloxanes; And the additive of 0.01wt%～7wt%, wherein said additive comprises filler, dripping inhibitor, thermo-stabilizer, photostabilizer, antioxidant, softening agent, static inhibitor, releasing agent, UV absorption agent, lubricant, pigment, dyestuff, tinting material or comprises the combination of two or more aforementioned substances.

Any that above-mentioned thermoplastic compounds can be arranged forms goods.

As known in the artly be, add acid or the acid salt of minute quantity in polycarbonate and the polycarbonate Alloys so that containment (quenching), passivation or the undesirable component of deactivation and make polycarbonate or polycarbonate Alloys stable.Adding of acid usually can make catalyst for ester exchange reaction, polycarbonate is synthetic or the condensation catalyst inactivation.Be known that equally and use following composition with deactivation or the undesirable composition of passivation, said composition comprises the combination of the ester of phosphoric acid and phosphoric acid.For example, referring to the people's such as Crosby US5608027, be incorporated herein by reference herein.The ester of acid, acid salt or acid uses in order to contain or passivation with minimum amount, but known polycarbonate can be degraded when with relatively large the use.

Term used herein " polycarbonate " refers to comprise the polymkeric substance of identical or different carbonate unit, perhaps comprises identical or different carbonate unit and the one or more of multipolymer (being Copolycarbonate) that is different from the unit of carbonic ether; Term " aliphatics " refers to that the valency that the non-annularity carbon atom arrangement by line style or branching forms is at least 1 alkyl; " aromatics " refers to that the valency that comprises at least one aryl is at least 1 group; " alicyclic " refers to that the valency that comprises non-aromatic ring-type carbon atom arrangement is at least 1 group; " alkyl " refers to the monovalence chain alkylene of straight chain or branching; " alkylidene group (alkylene) " refers to the divalence chain alkylene of straight chain or branching; The divalence chain alkylene of " alkylidene " straight chain or branching, two valence link is on single common carbon atom; " alkenyl " refers to the monovalence alkyl of straight chain or branching, and its at least two carbon atoms connect by carbon-carbon double bond; " cycloalkyl " refers to non-aromatic monovalence alicyclic alkyl, and it has at least three carbon atoms, has at least one degree of unsaturation; " cycloalkylidene " refers to non-aromatic divalence alicyclic alkyl, and it has at least three carbon atoms, has at least one degree of unsaturation; " aryl " refers to monovalence aromatics phenyl ring group, perhaps refers to be fused to the phenyl ring system group (radical system) of the optional replacement at least one optional phenyl ring that replaces; " aromatic group " refers to comprise at least one aryl and valency is at least 1 group; The example of aromatic group comprises phenyl, pyridyl, furyl, thienyl, naphthyl etc.; " arylidene " refers to the phenyl ring divalent group or is fused to the phenyl ring system divalent group of at least one optional phenyl ring that replaces; " alkaryl " refers to substitute onto the alkyl as defined above on aryl as defined above; " aralkyl " refers to substitute onto the aryl as defined above on alkyl as defined above; " alkoxyl group " refers to the alkyl as defined above that is connected with adjacent group by oxygen groups; " aryloxy " refers to the aryl as defined above that is connected with adjacent group by oxygen groups; The modifier " approximately " that uses together with quantity comprises the value of declaring, and has the implication (for example, comprising the degree of error relevant with the measurement of specific quantity) of defined in context; " optional " or " randomly " refers to, event or the situation described subsequently can occur or can not occur, the material of perhaps pointing out subsequently can exist or can not exist, and this description comprises when this event or situation occur or this material exists situation with when this event or situation does not occur or the non-existent situation of this material; And " directly key ", when as structure variable explanation a part of, refer to directly connect with the substituting group of being connected before the variable as " directly key ".

In this article, compound adopts standardized denomination to describe.For example, be not interpreted as the appointed key of its valency by the optional position that group replaced of any appointment or hydrogen atom is filled.The dash between two letters or symbol (" ") is not used for representing substituent tie point.For example ,-CHO is that the carbon by carbonyl (C=O) connects.Singulative " one (a) ", " one (an) " and " being somebody's turn to do (the) " comprise a plurality of indicators, unless context conclusivelys show in addition.The end points of mentioning all scopes of identical characteristics or component all can be combined independently and comprise mentioned end points.All reference are all incorporated this paper by reference into.Term " first ", " second " etc. do not represent any order, quantity or importance herein, but are used for distinguishing a kind of key element and another kind of key element.The modifier " approximately " that uses together with quantity comprises the value of declaring, and has the implication (for example, comprising the degree of error relevant with the measurement of specific quantity) of defined in context.

The component of term used herein " polycarbonate " and " polycarbonate resin " mean to have formula (1) carbonic ether repeated structural unit:

Wherein at least about the R of 60% sum ¹Group is the aromatics organic group, and all the other are aliphatic, alicyclic or aromatic group.In one embodiment, each R ¹Being the aromatics organic group, is for example the group of formula (2):

-A ¹-Y ¹-A ²- (2)

A in formula ¹And A ²The divalence of respectively doing for oneself monocyclic aryl, Y ¹To have one or two to separate A ¹And A ²The bridge joint group of atom.In exemplary embodiment, an atom separates A ¹And A ²Illustrative and the limiting examples of the type group be-O-,-S-, and-S (O)-,-S (O) ₂-,-C (O)-, methylene radical, cyclohexylmethylene, 2-[2.2.1]-two ring forks in heptan, ethylidene, isopropylidene, new pentylidene, cyclohexylidene, cyclopentadecane fork, cyclododecane fork, and Buddha's warrior attendant alkylidene.Bridge joint group Y ¹Can be alkyl or saturated hydrocarbyl such as methylene radical, cyclohexylidene, or isopropylidene.

But polycarbonate through type HO-R ¹The surface reaction preparation of the dihydroxy compound of-OH, described dihydroxy compound comprises the dihydroxy compound of formula (3):

HO-A ¹-Y ¹-A ²-OH (3)

Y in formula ¹, A ¹And A ²Same as above.Two phenolic compound that also comprise general formula (4):

R wherein ^aAnd R ^bRepresent separately halogen atom or monovalence alkyl, and can be identical or different; P and q are 0～4 integer independently of one another; And X ^aRepresent one of group of formula (5):

R wherein ^cAnd R ^dRepresent independently of one another hydrogen atom or monovalence straight chain or cyclic hydrocarbon group, and R ^eBe bivalent hydrocarbon radical.

some illustrative and the limiting examples of suitable dihydroxy compound comprise following: Resorcinol, 4-bromine Resorcinol, Resorcinol, 4, 4 '-dihydroxybiphenyl, 1, the 6-dihydroxy naphthlene, 2, the 6-dihydroxy naphthlene, two (4-hydroxy phenyl) methane, two (4-hydroxy phenyl) ditan, two (4-hydroxy phenyl)-1-naphthyl methane, 1, 2-two (4-hydroxy phenyl) ethane, 1, 1-two (4-hydroxy phenyl)-1-diphenylphosphino ethane, 2-(4-hydroxy phenyl)-2-(3-hydroxy phenyl) propane, two (4-hydroxy phenyl) phenylmethane, 2, 2-two (4-hydroxyl-3-bromophenyl) propane, 1, 1-two (hydroxy phenyl) pentamethylene, 1, 1-two (4-hydroxy phenyl) hexanaphthene, 1, 1-two (4-hydroxy phenyl) iso-butylene, 1, 1-two (4-hydroxy phenyl) cyclododecane, trans-2, 3-two (4-hydroxy phenyl)-2-butylene, 2, 2-two (4-hydroxy phenyl) diamantane, (α, α '-two (4-hydroxy phenyl) toluene, two (4-hydroxy phenyl) acetonitrile, 2, 2-two (3-methyl-4-hydroxy phenyl) propane, 2, 2-two (3-ethyl-4-hydroxy phenyl) propane, 2, 2-two (3-n-propyl-4-hydroxy phenyl) propane, 2, 2-two (3-sec.-propyl-4-hydroxy phenyl) propane, 2, 2-two (3-sec-butyl-4-hydroxy phenyl) propane, 2, 2-two (3-tert-butyl-hydroxy phenyl) propane, 2, 2-two (3-cyclohexyl-4-hydroxy phenyl) propane, 2, 2-two (3-allyl group-4-hydroxy phenyl) propane, 2, 2-two (3-methoxyl group-4-hydroxy phenyl) propane, 2, 2-two (4-hydroxy phenyl) HFC-236fa, 1, 1-two chloro-2, 2-two (4-hydroxy phenyl) ethene, 1, 1-two bromo-2, 2-two (4-hydroxy phenyl) ethene, 1, 1-two chloro-2, 2-two (5-phenoxy group-4-hydroxy phenyl) ethene, 4, 4 '-dihydroxy benaophenonel, 3, 3-two (4-hydroxy phenyl)-2-butanone, 1, 6-two (4-hydroxy phenyl)-1, the 6-hexanedione, ethylene glycol bisthioglycolate (4-hydroxy phenyl) ether, two (4-hydroxy phenyl) ether, two (4-hydroxy phenyl) thioether, two (4-hydroxy phenyl) sulfoxide, two (4-hydroxy phenyl) sulfone, 9, 9-two (4-hydroxy phenyl) fluorenes, 2, 7-dihydroxyl pyrene, 6, 6 '-dihydroxyl-3, 3, 3 ', 3 '-tetramethyl-spiral shell (two) indane (" the full bis-phenol of spirobiindene "), 3, 3-two (4-hydroxy phenyl) phthalide, 2, 6-dihydroxyl dibenzo-p-dioxin, 2, 6-one dihydroxyl thianthrene, 2, 7-dihydric phenol flavine (phenoxathin), 2, 7-dihydroxyl-9, 10-dimethyl azophenlyene, 3, 6-dihydroxyl diphenylene-oxide, 3, 6-dihydroxyl dibenzothiophen, 2, 7-dihydroxyl carbazole, 3, 3-two (4-hydroxy phenyl) benzo [C] pyrrolidone, 2-phenyl-3, 3-two (4-hydroxy phenyl) benzo [C] pyrrolidone (PPPBP) etc., and the combination that comprises at least a aforementioned dihydroxy compound.

the specific examples of the bisphenol cpd type of available formula (3) expression comprises: 1,1-two (4-hydroxy phenyl) methane, 1,1-two (4-hydroxy phenyl) ethane, 2,2-two (4-hydroxy phenyl) propane (being hereinafter " dihydroxyphenyl propane " or " BPA "), 2,2-two (4-hydroxy phenyl) butane, 2,2-two (4-hydroxy phenyl) octane, 1,1-two (4-hydroxy phenyl) propane, 1,1-two (4-hydroxy phenyl) normal butane, 2,2-two (4-hydroxyl-1-aminomethyl phenyl) propane, and 1,1-two (4-hydroxyl-tert-butyl-phenyl) propane.Also can use the combination that comprises at least a aforementioned dihydroxy compound.

Also can use branched polycarbonate, and the blend that comprises linear polycarbonate and branched polycarbonate.Branched polycarbonate can prepare by add branching agent between polymerization period.For example these branching agents comprise polyfunctional organic compound, and it comprises at least three and is selected from following functional group: hydroxyl, carboxyl, carboxylic acid anhydride, halo formyl radical, and the combination of aforementioned functional groups.Specific examples comprises trimellitic acid, trimellitic acid 1,2-anhydride, benzene three acyl chlorides partially; three p-hydroxybenzene ethane, isatin-diphenol, triphenol TC (1; 3; 5-three ((p-hydroxy phenyl) sec.-propyl) benzene), triphenol PA (4 (4 (1,1-two (p-hydroxy phenyl)-ethyl) α; α-dimethylbenzyl) phenol); 4-chloroformyl phthalic anhydride, trimesic acid, and benzophenone tetracarboxylic acid.Branching agent can polycarbonate the amount of approximately 0.05wt%～2.0wt% add.All types of polycarbonate terminal groups all can be used for polycarbonate, and condition is the needed character of this not remarkably influenced of end group thermoplastic compounds.

" polycarbonate " used herein and " polycarbonate resin " also comprise the blend of polycarbonate and other multipolymer that comprises the chain carbonic ester unit.Concrete suitable copolymerizable thing is polyestercarbonate, also is referred to as copolyesters-polycarbonate.This multipolymer except the carbonic ether repeating chain unit of formula (1), also comprises the repeating unit of following formula (6):

Wherein D is the divalent group that comes from dihydroxy compound, and can be for example C _2-10Alkylidene group, C _6-20Alicyclic group, C _6-20Aromatic group or polyalkylene oxides group, wherein alkylidene group comprises 2 to approximately 6 carbon atoms, specifically 2,3 or 4 carbon atoms; Reaching T is the divalent group that comes from dicarboxylic acid, and can be for example C _2-10Alkylidene group, C _6-20Alicyclic group, C _6-20Alkyl aromatic group, perhaps C _6-20Aromatic group.

In one embodiment, D is C _2-6Alkylidene group.In another embodiment, D is for coming from the dihydroxy aromatic compounds of following formula (7):

Each R wherein ^fBe halogen atom independently, C _1-10Alkyl, perhaps C _1-10The halo alkyl; And n is 0～4.Halogen is generally bromine.Can comprise Resorcinol by the example of the compound of formula (7) expression, the resorcinol compound that replaces such as oreinol diphenol, 5-ethyl resorcinol, 5-propyl group Resorcinol, 5-butyl Resorcinol, 5-tert-butyl resorcin, 5-phenyl Resorcinol, 5-cumyl Resorcinol, 2,4,5,6-tetrafluoro Resorcinol, 2,4,5,6-tetrabromo Resorcinol etc.; Pyrocatechol; Quinhydrones; The quinhydrones such as the 2-toluhydroquinone that replace, 2-ethyl quinhydrones, 2-propyl group quinhydrones, 2-butylhydroquinone, TBHQ, 2-phenyl quinhydrones, 2-cumyl quinhydrones, 2,3,5,6-duroquinol, 2,3,5,6-tetra-tert quinhydrones, 2,3,5,6-tetrafluoro quinhydrones, 2,3,5,6-tetrabromo quinhydrones etc.; And the combination that comprises at least a aforesaid compound.

The example that can be used for preparing the aromatic dicarboxylic acid of described polyester comprises: m-phthalic acid or terephthalic acid, and 1,2-two (p-carboxyl phenyl) ethane, 4,4 '-the dicarboxyl diphenyl ether, 4,4 '-diphenic acid, and comprise the combination of at least a aforementioned acid.Also can have the acid that comprises condensed ring, for example Isosorbide-5-Nitrae-, 1,5-or 2,6-naphthalene dicarboxylic acids.Concrete dicarboxylic acid is terephthalic acid, m-phthalic acid, naphthalene dicarboxylic acids, cyclohexane dicarboxylic acid, or its combination.Concrete dicarboxylic acid comprises the mixing of m-phthalic acid and terephthalic acid, and wherein the weight ratio of terephthalic acid and m-phthalic acid is approximately 10: 1 to approximately 0.2: 9.8.In another embodiment, D is C _2-6Alkylidene group, T are to phenylene, metaphenylene, naphthalene, divalence alicyclic group or its mixing.This kind polyester comprises poly-(terephthalic acid alkylene ester).

In one specific embodiment, described polycarbonate is the type homopolymer that comes from dihydroxyphenyl propane, wherein A ¹And A ²Respectively do for oneself to phenylene, Y ¹Be isopropylidene.

Suitable polycarbonate can be by the preparation such as the method such as interfacial polymerization and melt polymerization.Although the reaction conditions of interfacial polymerization can change, but exemplary method generally includes dissolving or disperse the dihydric phenol reactant in caustic soda or the Pian Zhuan caustic potash flakes aqueous solution, the gained mixture is added in suitable and the immiscible solvent medium of water, and under controlled pH (according to appointment 8～10) condition and suitable catalyzer (as triethylamine) or phase-transfer catalyst exist, this reactant is contacted with carbonate precursor.The most frequently used comprises methylene dichloride, 1,2-ethylene dichloride, chlorobenzene, toluene etc. with the immiscible solvent of water.Suitable carbonate precursor comprises for example carbonyl halide such as carbonyl bromide or carbonyl chloride, perhaps the bishaloformate (as the bishaloformate of ethylene glycol, neopentyl glycol, polyoxyethylene glycol etc.) of the bishaloformate of haloformate such as dihydric phenol (as the bischloroformate of dihydroxyphenyl propane, quinhydrones etc.) or glycol.Also can use the combination of the carbonate precursor that comprises at least a aforementioned type.

Available phase-transfer catalyst has formula (R ³) ₄Q ⁺The catalyzer of X, wherein each R ³Be identical or different C _1-10Alkyl; Q is nitrogen or phosphorus atom; X is halogen atom or C _1-8Alkoxyl group or C _6-188Aryloxy.Suitable phase-transfer catalyst comprises, for example, and [CH ₃(CH ₂) ₃] ₄NX, [CH ₃(CH ₂) ₃] ₄PX, [CH ₃(CH ₂) ₅] ₄NX, [CH ₃(CH ₂) ₆] ₄NX, [CH ₃(CH ₂) ₄] ₄NX, CH ₃[CH ₃(CH ₂) ₃] ₃NX, and CH ₃[CH ₃(CH ₂) ₂] ₃NX, wherein X is Cl ^-, Br ^-, C _1-8Alkoxyl group or C _6-188Aryloxy.The significant quantity of phase-transfer catalyst can be about 0.1wt%～l0wt%, based on the bis-phenol weight in the phosgenation mixture.In another embodiment, the significant quantity of phase-transfer catalyst can be about 0.5wt%～2wt%, based on the bis-phenol weight in the phosgenation mixture.

As selection, can prepare polycarbonate with melt process.Usually, in melt polymerization method, can be prepared as follows polycarbonate: be used to form uniform dispersion In mixing machine, twin screw extruder etc., under molten state and transesterification catalyst existence, dihydroxy reactants and diaryl carbonate such as diphenyl carbonate are reacted jointly.By distillation, remove the volatility monohydric phenol from the frit reaction thing, and go out polymkeric substance with the isolated in form of the residuum of melting.

Polycarbonate resin also can prepare by interface polymerization reaction.Can, sometimes even preferably use the reactive derivatives of acid rather than utilize dicarboxylic acid itself, the reactive derivatives of described acid is acyl halide, particularly acyl group dichloride and acyl group dibromide accordingly for example.Therefore, for example isophthaloyl dichloro, tere-phthaloyl dichloride and composition thereof be can use, rather than m-phthalic acid, terephthalic acid or its mixture used.

Except above-mentioned polycarbonate, can also use the combination of polycarbonate and other thermoplastic polymer, for example the combination of polycarbonate and/or Copolycarbonate and polyester.It is used herein that " combination " comprises mixture, blend, alloy etc.Suitable polyester comprises the repeating unit of formula (6), and can be for example poly-(alkylene dicarboxylic acids ester), liquid crystal polyester, and polyester copolymer.Can also use wherein be mixed with branching agent (as have three or the glycol of a plurality of hydroxyls or three or polyfunctional carboxylic acid) branched polyester.And, sometimes according to the end-use of composition, have acid and the hydroxyl end groups of different concns on preferred polyester.

In one embodiment, use poly-(terephthalic acid alkylene ester).The specific examples of suitable poly-(terephthalic acid alkylene ester) has poly-(ethylene glycol terephthalate) (PET), poly-(terephthalic acid 1, the 4-butanediol ester) (PBT), gather ((ethylene naphthalate)) (PEN), gather (naphthalic acid butanediol ester) (PBN), gather (propylene glycol ester terephthalate) (PPT), gather (terephthalic acid cyclohexanedimethanol ester) (PCT), and comprise the combination of at least a aforementioned polyester.Also expection, the copolyesters that the unit that above-mentioned polyester and a small amount of 0.5wt%～10wt% according to appointment come from aliphatic diacid and/or aliphatic polyol is made.

Also can use blend and/or the mixture of more than a kind of polycarbonate.For example, high workability and low flow polycarbonate can be blended together.

Described thermoplastic compounds comprises that further one or more impact modifier components are to improve the shock resistance of thermoplastic compounds.These impact modifiers can comprise elastomer-modified graft copolymer, this elastomer-modified graft copolymer comprise (i) Tg lower than approximately 10 ℃, more specifically lower than approximately-10 ℃ or the elasticity of approximately-40 ℃ to-80 ℃ (being also rubber-like) polymeric matrix (substrate) more especially, and (ii) be grafted to rigid polymer upper strata (superstrate) on elastomeric polymer matrix.Be known that elastomer-modified graft copolymer can be by being prepared as follows: at first elastomeric polymer is provided, then makes the formation monomer (one or more) of hard phase carry out polymerization and obtain graft copolymer under elastomerics exists.Grafts can be used as grafted branches or is connected on elastomer core as housing.Housing can be only that physical package seals core, and perhaps housing can partially or substantially completely be grafted on core.

Suitable material as the elastomerics phase comprises, for example, and conjugated diene rubber; Conjugated diolefine and the multipolymer that is less than about 50wt% copolymerizable monomer and forms; Olefinic rubber is ethylene propylene copolymer (EPR) or ethylene-propylene-diene monomer rubber (EPDM) for example; Ethylene-vinyl acetate rubber; Silicon rubber; Elasticity (methyl) vinylformic acid C _1-8Alkyl ester; (methyl) vinylformic acid C _1-8The elastocopolymer that alkyl ester and divinyl and/or vinylbenzene form; Perhaps comprise at least a aforementioned elastomeric combination.

The conjugate diene monomer that is suitable for preparation elastomerics phase is the monomer of formula (8):

Each X wherein ^bHydrogen, C independently ₁-C ₅Alkyl etc.The example of available conjugate diene monomer is divinyl, isoprene, 1,3-heptadiene, methyl isophthalic acid, 3-pentadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1.3-pentadiene; 1,3-and 2,4-hexadiene etc., and the mixture that comprises at least a aforementioned conjugate diene monomer.Concrete conjugated diene homopolymers comprises polyhutadiene and polyisoprene.

Can also use the multipolymer of conjugated diene rubber, for example can carry out with the monomer of its copolymerization by conjugated diolefine and one or more those multipolymers that free radical water emulsion polymerization prepares.The monomer that is suitable for carrying out with conjugated diolefine copolymerization comprises the mono vinyl aromatic monomer that contains the fused aromatic rings structure, such as vinyl naphthalene, vinyl anthracene etc., the perhaps monomer of formula (9):

Each X wherein ^cHydrogen, C independently ₁-C ₁₂Alkyl, C ₃-C ₁₂Cycloalkyl, C ₆-C ₁₂Aryl, C ₇-C ₁₂Aralkyl, C ₇-C ₁₂Alkaryl, C ₁-C ₁₂Alkoxyl group, C ₃-C ₁₂Cycloalkyloxy, C ₆-C ₁₂Aryloxy, chlorine, bromine or hydroxyl; And R is hydrogen, C ₁-C ₅Alkyl, bromine or chlorine.The example of the mono vinyl aromatic monomer that is suitable for using comprises vinylbenzene, 3-vinyl toluene, 3,5-diethylbenzene ethene, 4-n-propylbenzene ethene, alpha-methyl styrene, Alpha-Methyl Vinyl toluene, α-chloro-styrene, bromstyrol, dichlorostyrene, Dowspray 9, tetrachlorobenzene ethene etc., and the combination that comprises at least a aforesaid compound.Vinylbenzene and/or alpha-methyl styrene can be used as can with the monomer of conjugate diene monomer generation copolymerization.

Other monomers that can carry out copolymerization with conjugated diolefine are the monomers of single ethene, the acrylamide or the Methacrylamide that replace of methylene-succinic acid, acrylamide, N-for example, maleic anhydride, maleimide, the N-alkyl-, aryl-or the maleimide of halogenated aryl-replacement, (methyl) glycidyl acrylate, and the monomer of general formula (10):

Wherein R is hydrogen, C ₁-C ₅Alkyl, bromine or chlorine; X ^dCyano group, C ₁-C ₁₂Alkoxy carbonyl, C ₁-C ₁₂Aryloxycarbonyl, hydroxycarbonyl group etc.The example of monomer shown in formula (10) comprises vinyl cyanide, ethyl acrylonitrile (ethacrylonitrile), methacrylonitrile, α-chloro-acrylonitrile, β-chloroacrylonitrile, α-bromopropylene nitrile, vinylformic acid, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) n-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) vinylformic acid n-propyl, (methyl) isopropyl acrylate, (methyl) 2-EHA etc., and the combination that comprises at least a aforementioned monomer.Monomer such as n-butyl acrylate, ethyl propenoate and 2-EHA is commonly used for and can carries out with conjugate diene monomer the monomer of copolymerization.Also can use the mixture of aforementioned mono-vinyl monomer and mono vinyl aromatic monomer.

Applicable suitable (methyl) acrylate monomer of making the elastomerics phase can be crosslinked, (methyl) vinylformic acid C _1-8Alkyl ester corpuscle emulsion (particulate emulsion) homopolymer or multipolymer, particularly vinylformic acid C _4-6Alkyl ester, such as n-butyl acrylate, tert-butyl acrylate, vinylformic acid n-propyl, isopropyl acrylate, 2-EHA etc., and the combination that comprises at least a aforementioned monomer.(methyl) vinylformic acid C _1-8Alkyl ester monomer optionally with up to the formula (8) of 15wt%, the comonomer of (9) or (10) mixes to carry out polymerization.The comonomer example includes but not limited to divinyl, isoprene, vinylbenzene, methyl methacrylate, methacrylic acid phenylester, methacrylic acid phenethyl ester (penethylmethacrylate), N-cyclohexyl acrylamide, vinyl methyl ether or vinyl cyanide, and the mixture that comprises at least a aforementioned comonomer.randomly, can there be the multifunctional cross-linking comonomer up to 5wt%, Vinylstyrene for example, aklylene glycol two (methyl) acrylate is glycol diacrylate for example, alkylidene group triol three (methyl) acrylate, polyester two (methyl) acrylate, bisacrylamide, triallyl cyanurate, triallyl isocyanurate, (methyl) allyl acrylate, diallyl maleate, diallyl fumarate, diallyl adipate, the triallyl of citric acid, the triallyl of phosphoric acid etc., and the combination that comprises at least a aforementioned linking agent.

Elastomerics can adopt by the method for mass polymerization, emulsion polymerization, suspension polymerization, solution polymerization process or combination continuously mutually, semi-batch or batch technology carry out polymerization, in conjunction with method for example body-suspension polymerization, emulsion-mass polymerization, body-solution polymerization process or other technology.The granularity of elastomeric matrices is not critical.For example, approximately 0.001 to approximately 25 microns, particularly approximately 0.01 to approximately 15 microns or even more especially approximately 0.1 can be used for polyrubber latex (lattices) based on emulsion to the about mean particle size of 8 microns.Approximately 0.5 to approximately 10 microns, particularly approximately 0.6 can be used for the rubber matrix of mass polymerization to the about granularity of 1.5 microns.Granularity can be measured by means of simple optical transmission method (light transmissionmethods) or capillary hydrodynamics chromatography (CHDF).Elastomerics can be particulate state, appropriately crosslinked conj ugated butadiene or vinylformic acid C mutually _4-6Alkyl ester rubber, and preferably it has the gel content greater than 70%.That same suitable is divinyl and vinylbenzene and/or vinylformic acid C _4-6The mixture of alkyl ester rubber.

The approximately 5wt% that elastomerics can account for mutually whole graft copolymers is to about 95wt%, and the approximately 20wt% that more specifically accounts for elastomer-modified graft copolymer is to about 90wt%, even more specifically approximately 40wt% is to about 85wt%, and remainder is hard grafting phase.

Elastomer-modified graft copolymer hard can carry out graft polymerization by the mixture that comprises mono vinyl aromatic monomer and optional one or more comonomers mutually and form under the existence of one or more elastomer polymer matrix.The mono vinyl aromatic monomer of above-mentioned formula (9) can be used for hard grafting phase, and it comprises vinylbenzene, alpha-methyl styrene, halogenated styrenes such as Dowspray 9, Vinyl toluene, vinyl-dimethyl benzene, butylstyrene, 4-Vinyl phenol, methoxy styrene etc. or comprises the combination of at least a aforementioned mono vinyl aromatic monomer.Suitable comonomer for example comprises, the monomer of above-mentioned mono-vinyl monomer and/or general formula (10).In one embodiment, R is hydrogen or C ₁-C ₂Alkyl, X ^dCyano group or C ₁-C ₁₂Alkoxy carbonyl.The specific examples that is applicable to the comonomer of hard phase comprises vinyl cyanide, ethyl acrylonitrile, methacrylonitrile, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) vinylformic acid n-propyl, (methyl) isopropyl acrylate etc., and the combination that comprises at least a aforementioned comonomer.

Mono vinyl aromatic monomer alters a great deal with comonomer comparing in hard grafting mutually, and this depends on the type of elastomeric matrices, the type of mono vinyl aromatic monomer (one or more), type and the desirable impact modifier performance of comonomer (one or more).Usually can comprise up to 100wt% firmly mutually mono vinyl aromatic monomer, particularly approximately 30 to about 100wt%, more especially approximately 50 to about 90wt% mono vinyl aromatic monomer, surplus is comonomer.

Based on the amount of existing elastomer modified polymer, can obtain simultaneously separation matrix or the external phase of rigid polymer or the multipolymer of not grafting together with elastomer-modified graft copolymer.Usually, based on the gross weight of impact modifier, this impact modifier comprise approximately 40wt% to the about elastomer-modified graft copolymer of 95wt% and approximately 5wt% to approximately 65wt% grafting (being total to) polymkeric substance.In another embodiment, gross weight based on impact modifier, this impact modifier comprise approximately 50wt% to about 85wt%, more especially approximately 75wt% to the about graft copolymer of 85wt% modified rubber, and also have an appointment 15wt% to about 50wt%, more especially approximately 15wt% to approximately 25wt% grafting (being total to) polymkeric substance.

The elastomer-modified impact modifier of another particular type comprises derived from following structural unit: i.e. at least a rubber monomer, formula H ₂C=C (R ^g) C (O) OCH ₂CH ₂R ^hShown in branched acrylate rubber monomer, wherein R ^gHydrogen or C ₁-C ₈Straight or branched hydrocarbyl group and R ^hSide chain C ₃-C ₁₆Hydrocarbyl group; The first grafting connects (graft link) monomer; The polymerisable organic materials that contains alkenyl; Be connected grafting and connect monomer.Rubber monomer can comprise, for example cyclosiloxane, tetraalkoxysilane, trialkoxy silane, (acryloxy) organoalkoxysilane, (mercaptoalkyl) organoalkoxysilane, vinyl alkoxy silane or allyl group organoalkoxysilane, separately or be combined with, for example decamethylcyclopentaandoxane, ten diformazan basic ring six siloxanes, trimethyl triphenyl cyclotrisiloxane, tetramethyl tetraphenyl cyclotetrasiloxane, tetramethyl-tetrem thiazolinyl cyclotetrasiloxane, octaphenylcyclotetrasiloxane, octamethylcyclotetrasiloxane and/or tetraethoxysilane.

Exemplary branched acrylate rubber monomer comprises isooctyl acrylate ester, vinylformic acid 6-Methyl Octyl ester, vinylformic acid 7-Methyl Octyl ester, vinylformic acid 6-methylheptyl ester etc., separately or be combined with.The polymerisable organic materials that contains alkenyl for example can be, the monomer of formula (9) or (10), for example vinylbenzene, alpha-methyl styrene, vinyl cyanide, methacrylonitrile, or (methyl) acrylate such as the methyl methacrylate of non-branching, 2-Ethylhexyl Methacrylate, methyl acrylate, ethyl propenoate, vinylformic acid n-propyl etc., separately or be combined with.

It can be (acryloxy) organoalkoxysilane, (mercaptoalkyl) organoalkoxysilane, vinyl alkoxy silane or allyl group organoalkoxysilane that at least a the first grafting connects monomer, separately or be combined with, for example (γ-methacryloxypropyl) (dimethoxy) methyl-monosilane and/or (3-sulfydryl propyl group) Trimethoxy silane.It is polyene ethylenically unsaturated compounds with at least one allyl group that at least a the second grafting connects monomer, for example allyl methacrylate(AMA), triallyl cyanurate or triallyl isocyanurate, separately or be combined with.

The silicon-acrylate impact modifier composition can prepare by emulsion polymerization, wherein, for example at least a rubber monomer approximately 30 ℃ to the about temperature of 110 ℃ at tensio-active agent for example under the existence of Witco 1298 Soft Acid, be connected monomer reaction with at least a the first grafting, thereby form silicone rubber latex.Perhaps, such as the ring octamethylcyclotetrasiloxane be connected with the tetraethoxy ortho-silicate cyclosiloxane can with is connected monomer reaction such as the first grafting such as (γ-methacryloxypropyl) methyl dimethoxysilanes, be the about extremely about silicon rubber of 2 microns of 100 nanometers thereby mean particle size is provided.Then at least a branched acrylate rubber monomer and silicone rubber particles generation polymerization, optional at cross-linking monomer under for example allyl methacrylate(AMA) exists, the polymerizing catalyst that producing free radical for example carries out polymerization under the existence of benzoyl peroxide.Then make this latex and the polymerisable organic materials that contains alkenyl and be connected grafting and be connected monomer reaction.The silicone-acrylate rubber of isolating grafting from aqueous phase by cohesion (processing with flocculation agent) mixes the latex particle of body, and is dried to fine powder, thereby prepares the silicone-acrylate rubber impact modifier compositions.This method usually can be used for prepared sizes be approximately 100 nanometers to the about silicon-acrylate impact modifier of 2 microns.

The method that becomes known for forming aforementioned elastomer-modified graft copolymer comprises substance law, emulsion method, suspension method and solution method, perhaps for example body-suspension method, emulsion-substance law, body-solution method or other technology of the method for combination adopts continuously, semi-batch or batch technology.

If need, the impact modifier of aforementioned type can prepare by the emulsion polymerisation process of alkali-free material, and basic material is such as C _6-30An alkali metal salt of lipid acid, such as sodium stearate, lithium stearate, sodium oleate, potassium oleate etc., alkaline carbonate, amine such as dodecyl-dimethyl amine, lauryl amine etc., and the ammonium salt of amine.These materials are commonly used for tensio-active agent in letex polymerization, but and the transesterify of catalysis polycarbonate and/or Degradation.Instead, ionic sulfuric ester (salt), sulphonate (salt) or phosphoric acid ester (salt) tensio-active agent can be used for preparing the elastomeric matrices part of impact modifier, particularly impact modifier.Suitable tensio-active agent for example comprises, C _1-22Alkyl or C _7-25Alkyl aryl sulfonate (salt), C _1-22Alkyl or C _7-25Alkyl aryl sulfate (salt), C _1-22Alkyl or C _7-25Silicon ester (salt) of alkyl aryl phosphate ester (salt), replacement and composition thereof.Concrete tensio-active agent is C _6-16, C particularly _8-12Alkyl sulfonic ester (salt).(the Rohm ﹠amp as Rohm ﹠ Haas Corp is described and be disclosed in to this emulsion polymerisation process; Haas) and in the multiple patent and document of this class company of General Electric Corporation (General Electric Company).Can use in practice above-mentioned any impact modifier, condition is its not an alkali metal salt, alkaline carbonate and other basic material of fatty acids.

The special impact modifier of this class is MBS (MBS) impact modifier, wherein adopts above-mentioned sulphonate (salt), sulfuric ester (salt) or phosphoric acid ester (salt) to prepare divinyl matrix as tensio-active agent.Other example of elastomer-modified graft copolymer also includes but not limited to except ABS and MBS, acrylonitrile-styrene-butyl acrylate (ASA), methyl methacrylate-acrylonitrile-butadiene-styrene (ABS) (MABS) and vinyl cyanide-ethylene-propylene-diene-vinylbenzene (AES).

In certain embodiments, impact modifier is the graftomer with high rubber content, is also that rubber content is more than or equal to the approximately 50wt% of graftomer, randomly more than or equal to the approximately 60wt% of graftomer.The amount of rubber is preferably the approximately 95wt% less than or equal to graftomer, randomly less than or equal to the 90wt% of graftomer.

Rubber forms the main chain of graftomer, and is preferably the polymkeric substance of the conjugated diolefine of formula (11):

X wherein ^eHydrogen, C ₁-C ₅Alkyl, chlorine or bromine.The example of available diene is divinyl, isoprene, 1,3-heptadiene, methyl isophthalic acid, 3-pentadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-pentadiene; 1,3-and 2,4-hexadiene, the divinyl that chlorine replaces and bromine replaces is dichloroprene, bromine divinyl, dibromo divinyl for example, comprises the mixture of at least a aforementioned diene etc.Preferred conjugated diolefine is divinyl.Also can use the multipolymer of conjugated diolefine and other monomer, such as the multipolymer of butadiene-styrene, the multipolymer of butadiene-acrylonitrile etc.Perhaps, main chain can be acrylic elastomer, such as a kind of based on n-butyl acrylate, ethyl propenoate, 2-EHA, comprise the rubber of the mixture etc. of at least a aforementioned monomer.In addition, in the acrylic elastomer main chain copolymerizable a small amount of diene to improve grafting.

After forming trunk polymer, under existing, trunk polymer makes grafted monomer generation polymerization.A kind of grafted monomer of preferred type is the monovinyl aromatic hydrocarbons of formula (12):

X wherein ^bAs defined above, X ^fHydrogen, C ₁-C ₁₀Alkyl, C ₁-C ₁₀Cycloalkyl, C ₁-C ₁₀Alkoxyl group, C ₆-C ₁₈Alkyl, C ₆-C ₁₈Aralkyl, C ₆-C ₁₈Aryloxy, chlorine, bromine etc.Example comprises vinylbenzene, 3-vinyl toluene, 3,5-diethylbenzene ethene, 4-n-propylbenzene ethene, alpha-methyl styrene, Alpha-Methyl Vinyl toluene, α-chloro-styrene, bromstyrol, dichlorostyrene, Dowspray 9, tetrachlorobenzene ethene, and comprise mixture of at least a aforesaid compound etc.

The grafted monomer that can carry out the second type of polymerization under main polymer chain exists is the acrylic monomer of formula (13):

X wherein ^bAs defined above, Y ²Cyano group, C ₁-C ₁₂Alkoxy carbonyl etc.The example of this acrylic monomer comprises vinyl cyanide, ethyl acrylonitrile, methacrylonitrile, α-chloro-acrylonitrile, β-chloroacrylonitrile, α-bromopropylene nitrile, β-bromopropylene nitrile, methyl acrylate, methyl methacrylate, ethyl propenoate, butyl acrylate, propyl acrylate, isopropyl acrylate, comprises the mixture of at least a aforementioned monomer etc.

Also can use the mixture of grafted monomer, so that graft copolymer to be provided.Preferred mixture comprises monovinyl aromatic hydrocarbons and acrylic monomer.Preferred graft copolymer comprises acrylonitrile-butadiene-styrene (ABS) (ABS) and methacrylonitrile-butadiene-styrene (MBS) resin.Suitable high rubber acrylonitrile-butadiene-styrene resin can be bought from General Electric Corporation (General Electric Company) Specification 131,336,338,360 and 415.

Composition also can comprise aromatic ethenyl copolymer, for example styrene based copolymer (also referred to as " polystyrene copolymer ").Term used herein " aromatic ethenyl copolymer " and " polystyrene copolymer " and " styrene based copolymer " comprise the polymkeric substance by the known method preparation of prior art, the known method of prior art comprises mass polymerization, suspension polymerization and emulsion polymerization, adopts at least a monovinyl aromatic hydrocarbons.Polystyrene copolymer can be random, block or graft copolymer.The example of monovinyl aromatic hydrocarbons comprise alkyl-, cycloalkyl-, aryl-, alkaryl-, aralkyl-, alkoxyl group-and the vinyl aromatic compounds of other replacement, with and combination.Specific examples comprises: vinylbenzene, 4-vinyl toluene, 3,5-diethylbenzene ethene, 4-n-propylbenzene ethene, alpha-methyl styrene, Alpha-Methyl Vinyl toluene, α-chloro-styrene, bromstyrol, dichlorostyrene, Dowspray 9, tetrachlorobenzene ethene etc., with and the combination.The preferred monovinyl aromatic hydrocarbons of using is vinylbenzene and alpha-methyl styrene.

Described composition also comprises aromatic ethenyl copolymer.Aromatic ethenyl copolymer comprises comonomer, such as vinyl monomer, acrylic monomer, maleic anhydride and derivative etc., with and the combination.Defined vinyl monomer is the aliphatic cpd with at least one polymerizable carbon-carbon double bond herein.When having two or more carbon-carbon double bonds, they can form conjugation each other, or really not so.Suitable vinyl monomer for example comprises, ethene, propylene, butylene (comprising 1-butylene, 2-butylene and iso-butylene), amylene, hexene etc.; 1,3-butadiene, 2-methyl isophthalic acid, 3-divinyl (isoprene), Isosorbide-5-Nitrae-pentadiene, 1,5-hexadiene etc.; With and the combination.

Acrylic monomer for example comprises, vinyl cyanide, ethyl acrylonitrile, methacrylonitrile, α-chloro-acrylonitrile, β-chloroacrylonitrile, α-bromopropylene nitrile and β-bromopropylene nitrile, methyl acrylate, methyl methacrylate, ethyl propenoate, butyl acrylate, propyl acrylate, isopropyl acrylate etc., with and composition thereof.

Maleic anhydride and its derivative for example comprise, maleic anhydride, maleimide, N-alkyl maleimide, N-aryl maleimide or alkyl-or the N-aryl maleimide of halogen-replacements etc., with and make up.

The amount of comonomer (one or more) in aromatic ethenyl copolymer can change.Yet contents level is normally approximately 2% to about 75% molecular fraction.In this scope, the molecular fraction of comonomer can be specifically at least 4%, and more specifically at least 6%.Equally in this scope, the molecular fraction of comonomer can be specifically up to approximately 50%, more especially up to approximately 25%, even more especially up to approximately 15%.Concrete polystyrene copolymer resins often comprises poly-(styrene-maleic anhydride) and poly-(styrene-acrylonitrile) that often is called " SAN " that is called " SMA ".

In one embodiment, aromatic ethenyl copolymer comprises: (a) aromatic vinyl monomer component and (b) cyanide vinyl monomer (cyanide vinyl monomer) component.(a) example of aromatic vinyl monomer component comprises alpha-methyl styrene, ortho-, meta-or p-vinyl toluene, vinyl-dimethyl benzene, monochlorostyrene, dichlorostyrene, phenyl-monobromide ethene, Dowspray 9, fluorobenzene ethene, p-tert-butylstyrene, ethyl styrene and vinyl naphthalene, and these materials can use separately or be combined with.(b) example of cyanide vinyl monomer component comprises vinyl cyanide and methacrylonitrile, and they can use separately or two or more are combined with.There is no particular restriction with (b) ratio of components to (a) in aromatic ethenyl copolymer, and this ratio should be selected according to described should being used for.Randomly, aromatic ethenyl copolymer can comprise: with the weighing scale of (a)+(b) in aromatic ethenyl copolymer, approximately 95wt% is to about (a) of 50wt%, and optional approximately 92wt% is to about (a) of 65wt%; Correspondingly with the weighing scale of (a)+(b) in aromatic ethenyl copolymer, approximately 5wt% is to about (b) of 50wt%, and optional approximately 8wt% is to about (b) of 35wt%.

The weight-average molecular weight of aromatic ethenyl copolymer (Mw) can be 30000 to 200000, and optional is 30000 to 110000, by gel permeation chromatography measurement.

The method of producing aromatic ethenyl copolymer comprises mass polymerization, solution polymerization process, suspension polymerization, body suspension polymerization and emulsion polymerization.In addition, resin that also can the independent copolymerization of blend.The alkali metal content of aromatic ethenyl copolymer can be about 1ppm or still less with the weighing scale of aromatic ethenyl copolymer, about 0.5ppm or still less randomly, for example about 0.1ppm or still less.And in the middle of basic metal, the content of sodium and potassium can be about 1ppm or still less in component (b), about 0.5ppm or still less randomly, for example about 0.1ppm or still less.

In one embodiment, aromatic ethenyl copolymer comprises " freedom " styrene-acrylonitrile copolymer (SAN), is not namely also the styrene-acrylonitrile copolymer that is grafted on other polymer chain.In one embodiment, free styrene-acrylonitrile copolymer can have 50000 to about 200000 molecular weight for the polystyrene standard molecular size range, and can comprise multiple vinylbenzene to the ratio of vinyl cyanide.For example, based on the gross weight meter of free SAN multipolymer, free SAN can comprise approximately 75wt% vinylbenzene and approximately 25wt% vinyl cyanide.Free SAN optionally exists by add the graft rubber impact modifier that comprises free SAN in composition, and/or free SAN can be independent of the impact modifier in composition and exist.

With the composition weight meter shown in embodiment herein, composition can comprise approximately 2wt% to about 25wt% free SAN, randomly approximately 2wt% to about 20wt% free SAN, for example approximately 5wt% to about 15wt% free SAN or randomly approximately 7.5wt% to about 10wt% free SAN.

Described composition also comprises at least a mineral filler.The non-exhaustive that is applicable to the mineral filler example of composition is enumerated and is included but not limited to, talcum, mica, wollastonite, clay etc.Also can use the combination of filler." mineral filler " comprises any synthetic and naturally occurring polycarbonate and polycarbonate Alloys toughener as term used herein, thereby it can obtain balanced physicals and polycarbonate or polycarbonate Alloys are degraded in conjunction with producing synergistic effect with acid or acid salt.

In one embodiment, described mineral filler is talcum.Can use any suitable talcum.In some embodiments, described talcum be size-grade distribution D50 less than 10 microns, optional less than 5 microns or less than the meticulous talcum of 3 microns.Talcum is commercially available and be known in the art.An example of suitable talcum is the talcum of commodity Jetfine 3CA by name, and its size-grade distribution D50 is approximately 1.1 microns, can obtain from Luzenac.

Described composition also comprises titanium dioxide (TiO ₂).This TiO ₂For having the coating TiO of the particular type coating that comprises silica or siloxanes ₂" coating (coated) " used herein means titanium dioxide and has at least a coating or the surface treatment that contains silicone or siloxanes, for example organo-siloxane.Described top coat or process can be organic or inorganic or above both.Also can there be other coating or processes as aluminum oxide." uncoated (uncoated) " used herein means titanium dioxide and do not apply with silicone or siloxanes, although can have other coating or process as aluminum oxide.Titanium dioxide is commercially available takes pride in multi-provider, as E.I.du Pont de Nemours company, and Kronos Worldwide International company and Millennium Chemicals and have different size.The example of commercially available suitable titanium dioxide includes but not limited to

2233,

2450 (all can obtain from Kronos Worldwide company) and

RL-91 (Millennium Chemicals).

Said composition also randomly comprises organic-hydride siloxane (organo-hydrosiloxane).Described organic-hydride siloxane has following formula:

R ₃-SiO-[RH-SiO] _n-Si-R ₃

Wherein R is hydrogen, C independently of one another ₁～C ₈Alkyl or C ₆～C ₁₂Aryl; N is 1 to approximately 50.In one embodiment, each R is methyl, and n is approximately 15～25, randomly approximately 20.Commercially available organic-example of hydride siloxane comprises the DF1040 from GE Bayer Silicones.

Organic-hydride siloxane can be also the multipolymer that comprises organic-hydride siloxane and polysiloxane.In some embodiments, the described multipolymer that comprises organic-hydride siloxane and polysiloxane comprise 10wt% at least organic-hydride siloxane, randomly at least 50wt% organic-hydride siloxane.

Polysiloxane in described multipolymer can be poly-alkylsiloxane, poly-aryl siloxanes, organopolysiloxane etc.This polysiloxane has following formula:

R ₃-SiO-[R ₂-SiO] _m-Si-R ₃

Wherein R is hydrogen, C independently of one another ₁～C ₈Alkyl or C ₆～C ₁₂Aryl; M is 1 to approximately 200.In one embodiment, described polysiloxane is polydimethylsiloxane (PDMS), and wherein each R is methyl.The example of commercially available polydimethylsiloxane comprises can be from SF96-1000 and the SF18-350 of GE Bayer Silicones acquisition.

If use the multipolymer that comprises organic-hydride siloxane and polysiloxane, this multipolymer can be the multipolymer that for example comprises polymethyl hydrogen siloxane (PMHS) and polydimethylsiloxane (PDMS) so.

Described composition randomly also comprises acid or acid salt.In one embodiment, acid or acid salt are mineral acid or inorganic acid salt.In one embodiment, acid is to comprise a kind of acid that contains phosphorus oxyacid (phosphorous containing oxy-acid).

In one embodiment, containing phosphorus oxyacid is that the many protons with general formula (14) contain phosphorus oxyacid:

H _m P _t O _n (14)

Wherein m and n respectively do for oneself 2 or larger; T is 1 or larger.

The example of the acid of formula (14) includes but not limited to, the acid shown in following formula: H ₃PO ₄, H ₃PO ₃And H ₃PO ₂In certain embodiments, acid comprises one of following: phosphoric acid, phosphorous acid, Hypophosporous Acid, 50, diphosphanetetroic acid, phospho acid, phosphonic acids, metaphosphoric acid, hexa metaphosphoric acid, thiophosphoric acid, fluoro phosphoric acid, two fluoro phosphoric acid, fluoro phosphorous acid, two fluoro phosphorous acid, fluoro Hypophosporous Acid, 50 or fluoro diphosphanetetroic acid.Perhaps, can use acid and acid salt such as sulfuric acid, sulphite, phosphoric acid one zinc, mono-calcium phosphate, monosodium phosphate.Acid and acid salt are preferred so to be selected so that it can be effectively with mineral filler (perhaps mineral filler and organic-hydride siloxane) thereby in conjunction with obtaining the balanced of synergistic effect and performances such as mobility and shock resistance in polycarbonate or polycarbonate Alloys.

Described thermoplastic compounds can comprise the various additives of usually incorporating resin combination or this type of blend into, and condition is that preferable additives makes not the significantly expected performance of this thermoplastic compounds of negative impact.Can use the mixture of additive.Can mix above-mentioned additive the suitable opportunity in being mixed for forming each composition process of composition.

If need to use other filler and/or toughener, condition is that they can further not make composition degrade.Suitable filler or toughener comprise any material that becomes known for these purposes.For example, suitable filler and toughener comprise silicate and SiO 2 powder such as pure aluminium silicate (mullite), synthetic calcium silicate, zirconium silicate, fused silica, crystallinity silicon-dioxide graphite, natural silica Sand etc.; Boron powder such as boron nitride powder, borosilicate powder etc.; Oxide compound is TiO for example ₂, aluminum oxide, magnesium oxide etc.; Calcium sulfate (its anhydride, dihydrate or trihydrate); Calcium carbonate such as chalk, Wingdale, marble, synthetic precipitated chalk etc.; Talcum comprises fibrous, module shape (modular), aciculiform, stratiform talcum etc.; Wollastonite; The surface-treated wollastonite; Glass sphere such as hollow and solid glass ball, silicate ball, cenosphere, aluminosilicate (flying dust microballon armosphere) etc.; Kaolin, comprise hard kaolin, soft kaolin, roasting kaolin, comprise various prior aries known in order to improve with the kaolin of the coating of polymeric matrix consistency etc.; Single crystal fibre or " whisker " such as silicon carbide, aluminum oxide, norbide, iron, nickel, copper etc.; Fiber (comprising continuous fibre and staple fiber) is asbestos, carbon fiber, glass fibre for example, for example E, A, C, ECR, R, S, D or NE glass, etc.; Sulfide such as moly-sulfide, zinc sulphide etc.; Barium compound such as barium titanate, barium ferrite, barium sulfate, barite etc.; Metal and metal oxide such as granular or fibrous aluminium, bronze, zinc, copper and mickel etc.; The silicon carbide of the filler of thin slice such as sheet glass, thin slice, aluminium diboride, aluminium flake, steel disc etc.; Fibrous packing, for example, short inorganic fibre as obtained by at least a blend that comprises pure aluminium silicate, aluminum oxide, magnesium oxide and calcium sulfate hemihydrate those etc.; Natural stuffing and strongthener are as the wood chip that obtains by pulverizing timber, fibrous product such as Mierocrystalline cellulose, cotton, sisal hemp, jute, starch, dust cork, xylogen, the rice hulls that grinds, corn, paddy shell etc.; Organic filler such as tetrafluoroethylene etc.; The organic fibre shape filler that strengthens, formed by the organic polymer that can form fiber, as poly-(ether ketone), polyimide, polybenzoxazole, poly-(diphenyl sulfide), polyester, polyethylene, aromatic polyamide, aromatic polyimide, polyetherimide, tetrafluoroethylene, acrylic resin, poly-(vinyl alcohol) etc.; And other filler and toughener such as mica, clay, feldspar, cigarette ash, inert silicate microballoon, quartz, quartzite, perlite, tripoli, diatomite, carbon black etc., perhaps comprise the combination of at least a aforementioned filler or toughener.

Described filler and toughener can apply the layer of metal material and be beneficial to conduction, or surface-treated with silane is to improve binding property and the dispersiveness to the polymer matrix resin.In addition, reinforcing filler can monofilament or the multifilament fiber form provide, and can use separately, perhaps for example construct by being total to braiding or core/skin, block form, orange type or matrix and fibril, or make the fiber combinations use of the known additive method of those skilled in the art and other types by fiber.Suitable common braiding structure is such as comprising glass fibre-carbon fiber, carbon fiber-aromatic polyimide (aromatic polyamide) fiber and aromatic polyimide fibre glass fibre etc.Fibrous packing provides such as being following form: fibrous reinforcement such as the 0-90 degree fabric of rove (rovings), weaving etc.; Nonwoven fibrous reinforce such as continuous strand sheet (continuous strand mat), chopped strand sheet (chopped strand mat), thin,tough silk yarn (tissue), paper and woollen blanket etc.; Or the three-dimensional woven reinforce, as braid (braids).Based on total composition meter of 100 weight parts, the consumption of the filler except described mineral filler is normally approximately 0 to about 50 weight parts, randomly approximately 1 to about 20 weight parts, is approximately 4 to about 15 weight parts in certain embodiments.

Described composition can be chosen blend and the multipolymer that comprises other polycarbonate wantonly, such as polycarbonate-polysiloxane copolymer, ester class etc.

Thermoplastic compounds can be chosen wantonly and comprise cycloaliphatic polyester resin.Described cycloaliphatic polyester resin comprises the polyester of (15) repeating unit that has formula:

At least one R wherein ¹⁵Or R ¹⁶It is the group that contains cycloalkyl.

Described polyester is condensation product, wherein R ¹⁵Residue or its chemical equivalence thing that has 6 to 20 carbon atoms and contain the glycol of aryl, alkane or naphthenic hydrocarbon, R ¹⁶That collateral condition is at least one R derived from decarboxylation residue or its chemical equivalence thing of the diacid that contains aryl, aliphatic series or naphthenic hydrocarbon of 6 to 20 carbon atoms ¹⁵Or R ¹⁶Alicyclic.In some embodiments, R ¹⁵And R ¹⁶All alicyclic.

Present cycloaliphatic polyesters is the condensation product of aliphatic diacid or chemical equivalence thing and aliphatic diol or chemical equivalence thing.Present cycloaliphatic polyesters can be formed by the mixture of aliphatic diacid and aliphatic diol, but must contain at least 50 % by mole of ring-type diacid and/or cyclic diols component, and remainder is linear aliphatic diacid and/or glycol if present.

Vibrin generally makes through condensation polymerization reaction or ester interchange polymerization reaction by glycol or diol equivalent thing component and diacid or diacid chemical equivalence thing component.

R ¹⁵And R ¹⁶Be preferably group of naphthene base, it is independently selected from following formula:

Preferred alicyclic group R ¹⁶Derived from Isosorbide-5-Nitrae-cyclohexyl diacid, most preferably it is the trans-isomer(ide) form greater than 70 % by mole.Preferred alicyclic group R ¹⁵Derived from Isosorbide-5-Nitrae-cyclohexyl uncle glycol Isosorbide-5-Nitrae-cyclohexyl dimethanol for example, most preferably it is the trans-isomer(ide) form greater than 70 % by mole.

Other glycol that can be used for preparing vibrin of the present invention is straight chain, branching or alicyclic alkanediol and can comprises 2 to 12 carbon atoms.The example of these glycol includes but not limited to ethylene glycol; Propylene glycol is also 1,2-and 1,3-PD; 2，2-dimethyl-1，3-propanediol; 2-ethyl, 2-methyl, 1,3-PD; 1,3-and 1,5-PD; Dipropylene glycol; The 2-methyl isophthalic acid, the 5-pentanediol; 1,6-hexylene glycol; The dimethanol naphthane, the dimethanol double-octane; 1,4 cyclohexane dimethanol and particularly its cis and trans-isomer(ide); TMCBD (TMCBD), triglycol; Decamethylene-glycol; And aforementioned any mixture.The preferred alicyclic diol or its chemical equivalence thing and particularly 1,4 cyclohexane dimethanol or its chemical equivalence thing of using is as diol component.

The chemical equivalence thing of glycol comprises the ester class, such as dialkyl esters, diaryl ester class etc.

The diacid that can be used for preparing aliphatic polyester resin of the present invention is preferably alicyclic diacid.This means the carboxylic acid that comprises with two carboxyls, wherein each carboxyl is connected to saturated carbon atom.Preferred diacid is the aliphatic acid of ring-type or dicyclo, for example naphthane dicarboxylic acid, norbornene dicarboxylic acids, double-octane dicarboxylic acid, Isosorbide-5-Nitrae-cyclohexane dicarboxylic acid or chemical equivalence thing, most preferably t-CHDA or chemical equivalence thing.Also can use as linear dicarboxylic acids such as hexanodioic acid, nonane diacid, dicarboxyl dodecylic acid and succsinic acids.

Cyclohexane dicarboxylic acid and its chemical equivalence thing can for example pass through cyclophane family's diacid and corresponding derivative such as m-phthalic acid, terephthalic acid or naphthalic acid, appropriate solvent such as water or acetic acid in, and adopt suitable catalyzer for example to be carried on that the rhodium on carrier carries out hydrogenization and makes such as carbon or aluminum oxide.They also can be by using the inertia liquid medium and adopting the palladium or the ruthenium catalyst that are carried on carbon or silicon-dioxide to make, and wherein phthalic acid is that part dissolves in described inertia liquid medium at least under reaction conditions.

Usually, obtained two kinds of isomer in hydrogenization, wherein hydroxy-acid group is in cis or trans position.Cis can be separated by crystallization with trans-isomer(ide), adopt or do not adopt solvent for example normal heptane all can, perhaps separate by distilling.Cis-isomeride often can be blended together better; But, have higher fusing point and Tc therefore can be preferred to trans-isomer(ide).Can use equally the mixture of cis and trans-isomer(ide) herein.

If use mixture or more than a kind of diacid or the glycol of isomer, can adopt the mixture of copolyesters or two kinds of polyester as cycloaliphatic polyester resin of the present invention.

The chemical equivalence thing of these diacid comprises the ester class, alkyl esters, for example dialkyl, diaryl ester, anhydrides, salt, chloride of acid, acid bromide etc.Preferred chemical equivalence thing comprises the dialkyl of alicyclic diacid, and most preferred chemical equivalence thing comprises sour dimethyl esters, particularly dimethyl-Isosorbide-5-Nitrae-hexanaphthene-dicarboxylic ester.

Preferred present cycloaliphatic polyesters is poly-(hexanaphthene-Isosorbide-5-Nitrae-Dimethylenecyclohexacompound-Isosorbide-5-Nitrae-dicarboxylic ester), and also referred to as poly-(Isosorbide-5-Nitrae-hexanaphthene-dimethanol-Isosorbide-5-Nitrae-dicarboxylic ester) (PCCD), it has the repeating unit of formula (16):

With reference to the general formula that proposes previously, for PCCD, R ¹⁵Be derived from 1,4 cyclohexane dimethanol; R ¹⁶It is the cyclohexane ring that is derived from cyclohexanedicarboxyester ester or its chemical equivalence thing.Preferred PCCD has suitable/transconfiguration formula.

Polyester reaction is carried out under molten state under appropriate suitable catalyzer exists usually, suitable catalyzer four (2-ethylhexyl) titanic acid ester for example, and catalytic amount is based on final product meter about 50 to 200ppm titaniums normally.

The second-order transition temperature (Tg) of preferred aliphatic polyester is higher than 50 ℃, more preferably higher than 80 ℃ and most preferably higher than approximately 100 ℃.

Herein same consider be above-mentioned band have an appointment 1 to about 50wt% derived from the polyester of the unit of polymkeric substance aliphatic acid and/or polymkeric substance aliphatic polyol in order to form copolyesters.Aliphatic polyol comprises glycol, for example PEG or poly-(butyleneglycol).These polyester can be made according to the instruction of for example United States Patent (USP) 2465319 and 3047539.

Described composition can further comprise the polycarbonate-polysiloxane copolymer that contains polycarbonate block and polydiorganosiloxane block.Polycarbonate block in multipolymer comprises the repeated structural unit of formula (1) as mentioned above, for example R wherein ¹Formula as above (2).These unit can come from the reaction of the dihydroxy compound of formula (3) as mentioned above.In one embodiment, dihydroxy compound is dihydroxyphenyl propane, wherein A ¹And A ²Respectively do for oneself to phenylene and Y ¹It is isopropylidene.

The polydiorganosiloxane block comprises the repeated structural unit (this paper is sometimes referred to as " siloxanes ") of formula (17):

Identical or different when wherein R occurs at every turn, and be C _1-13Any monovalent organic radical group.For example, R can be C ₁-C ₁₃Alkyl group, C ₁-C ₁₃Alkoxy base, C ₂-C ₁₃Kiki alkenyl group, C ₂-C ₁₃Alkenyl oxy group, C ₃-C ₆Group of naphthene base, C ₃-C ₆Cycloalkyloxy group, C ₆-C ₁₀Aromatic yl group, C ₆-C ₁₀Aryloxy group, C ₇-C ₁₃Aromatic alkyl group, C ₇-C ₁₃Aralkoxy group, C ₇-C ₁₃Alkylaryl group or C ₇-C ₁₃The aryloxy alkyl group.The combination of aforementioned R group also can be used for identical multipolymer.

D value can alter a great deal in formula (17), this type that depends on each component in thermoplastic compounds and relative consumption, required composition properties and similar Consideration.Usually, the mean value of D can be 2 to approximately 1000, particularly approximately 2 to approximately 500, more especially approximately 5 to approximately 100.D has approximately 10 to about 75 mean value in one embodiment, and D has approximately 40 to about 60 mean value in another embodiment.If D has lower value, for example lower than approximately 40, preferably use relatively a large amount of polycarbonate-polysiloxane copolymers.On the contrary, if D has high value, for example greater than approximately 40, need to use relatively a small amount of polycarbonate-polysiloxane copolymer.

Can use the combination of first and second (or more) polycarbonate-polysiloxane copolymers, wherein the D mean value of the first multipolymer is lower than the D mean value of the second multipolymer.

In one embodiment, the polydiorganosiloxane block is provided by the repeated structural unit of formula (18):

Wherein D as defined above; Each R can be identical or different, and as defined above; Ar can be identical or different, and be that replace or unsubstituted C ₆-C ₃₀Arylene group, wherein this key is connected directly to the aromatics part.Ar group suitable in formula (9) can be derived from C ₆-C ₃₀Dihydroxyl arylene compound, for example the dihydroxyl arylene compound of following formula (3), (4) or (7).Also can use the combination that comprises at least a aforementioned dihydroxyl arylene compound.the specific examples of suitable dihydroxyl arylene compound is 1, 1-two (4-hydroxy phenyl) methane, 1, 1-two (4-hydroxy phenyl) ethane, 2, 2-two (4-hydroxy phenyl) propane, 2, 2-two (4-hydroxy phenyl) butane, 2, 2-two (4-hydroxy phenyl) octane, 1, 1-two (4-hydroxy phenyl) propane, 1, 1-two (4-hydroxy phenyl) normal butane, 2, 2-two (4-hydroxyl-1-aminomethyl phenyl) propane, 1, 1-two (4-hydroxy phenyl) hexanaphthene, two (4-hydroxy phenyl thioethers) (bis (4-hydroxyphenyl sulphide)) and 1, 1-two (4-hydroxyl tert-butyl-phenyl) propane.Also can use the combination that comprises at least a aforementioned dihydroxy compound.

These unit can be derived from the corresponding dihydroxy compound shown in following formula (19):

Wherein Ar and D are as mentioned above.These compounds are further described in the people's such as Kress United States Patent (USP) 4746701.The compound of this formula can be under condition of phase transition by dihydroxyl arylene compound and for example α, the reaction of ω-diacetoxy polydiorganosiloxane and making.

The polydiorganosiloxane block comprises the repeated structural unit of formula (20) in another embodiment:

Wherein R and D are as defined above.R in formula (20) ²Divalence C ₂-C ₈Aliphatic group.In formula (20), each M can be identical or different, and can be halogen, cyano group, nitro, C ₁-C ₈Alkyl sulfide, C ₁-C ₈Alkyl, C ₁-C ₈Alkoxyl group, C ₂-C ₈Alkenyl, C ₂-C ₈Alkenyloxy group, C ₃-C ₈Cycloalkyl, C ₃-C ₈Cycloalkyloxy, C ₆-C ₁₀Aryl, C ₆-C ₁₀Aryloxy, C ₇-C ₁₂Aralkyl, C ₇-C ₁₂Aralkoxy, C ₇-C ₁₂Alkaryl or C ₇-C ₁₂Aryloxy alkyl, wherein each n is 0,1,2,3 or 4 independently.

In one embodiment, M is bromine or chlorine, and alkyl group is methyl, ethyl or propyl group for example, and alkoxy base is methoxyl group, oxyethyl group or propoxy-for example, perhaps for example phenyl, chloro-phenyl-or tolyl of aromatic yl group; R ²Dimethylene, trimethylene or tetramethylene group; R is C _1-8Alkyl, haloalkyl is trifluoro propyl for example, cyano group alkyl, or aryl for example phenyl, chloro-phenyl-or tolyl.In another embodiment, R is methyl, or the mixture of methyl and trifluoro propyl, or the mixture of methyl and phenyl.M is methoxyl group in yet another embodiment, and n is 1, R ²Divalence C ₁-C ₃Aliphatic group, and R is methyl.

These unit can be derived from corresponding dihydroxyl polydiorganosiloxane (21):

Wherein R, D, M, R ²With n as mentioned above.

This polysiloxanediol can be by formula (22) below siloxanes hydride and aliphatic unsaturated monohydric phenol between implement platinum catalysis addition reaction prepare:

Wherein R and D such as front are defined.Suitable aliphatic unsaturated monohydric phenol comprises, for example, and oxymethoxyallylbenzene, the 2-alkylphenol, 4-allyl group-2-methylphenol, 4-allyl group-2-phenylphenol, 4-allyl group-2-bromophenol, 4-allyl group-2-tert.-butoxy phenol, 4-phenyl-2-phenylphenol, 2-methyl-4-propylphenol, 2-allyl group-4,6-xylenol, 2-allyl group-4-bromo-6-methylphenol, 2-allyl group-6-methoxyl group-4-methylphenol, and 2-allyl group-4, the 6-xylenol.Also can use the mixture that comprises at least a aforementioned phenols.

Polycarbonate-polysiloxane copolymer can prepare by the reaction of biphenol polysiloxane (21) with the dihydroxy aromatic compounds of carbonate source and formula (3), randomly reacts under phase-transfer catalyst as above exists.Suitable condition is similar to those the available conditions in polycarbonate of making.For example, lower than 0 ℃～approximately at the temperature of 100 ℃, preferred approximately 25 ℃～approximately make multipolymer by phosgenation under 50 ℃.Because this reaction is thermopositive reaction, can utilize the speed of adding phosgene to control temperature of reaction.The amount of required phosgene depends on the amount of dihydroxy reactants usually.Alternatively, under molten state, make dihydroxyl monomer and diaryl carbonate such as diphenyl carbonate under the existence of above-mentioned transesterification catalyst, coreaction occur and prepare polycarbonate-polysiloxane copolymer.

In the preparation of polycarbonate-polysiloxane copolymer, select the amount of the poly-diorganosiloxane of dihydroxyl in order to the poly-diorganosiloxane unit of aequum in multipolymer is provided.The amount of poly-diorganosiloxane unit can change by wide region, can be namely the about 99wt% polydimethylsiloxane of 1wt%～approximately, perhaps other poly-diorganosiloxane of equimolar amount, and remainder is carbonate unit.Therefore determine this concrete consumption according to the type of each component in physicals, D value (in 2～approximately 1000 scope) and the thermoplastic compounds of desirable thermoplastic compounds with relative consumption, the type of each component and relative consumption comprise type and consumption, the type of polycarbonate-polysiloxane copolymer and type and the consumption of consumption and any other additive of the type of polycarbonate and consumption, impact modifier.The suitable consumption of the poly-diorganosiloxane of dihydroxyl can determine need not too much experiment according to the principle of this paper instruction by those of ordinary skills.For example, can select the consumption of the poly-diorganosiloxane of dihydroxyl in order to prepare such multipolymer, it comprises approximately the 75wt% of 1wt%～approximately or about 50wt% polydimethylsiloxane or the another kind of polydiorganosiloxane of equimolar amount of 1wt%～approximately.In one embodiment, multipolymer comprises approximately the 40wt% of 5wt%～approximately, the about 25wt% polydimethylsiloxane of 5wt%～approximately randomly, the perhaps poly-diorganosiloxane of the another kind of equimolar amount, and remainder is polycarbonate.In specific embodiment, multipolymer can comprise approximately 20wt% siloxanes.

In multiple embodiments, described thermoplastic compounds comprises approximately 30wt% to the about polycarbonate resin of 89.5wt%; Randomly approximately 40wt% to the about polycarbonate of 89.5wt%; The about polycarbonate of 50wt% to 85wt% randomly.This thermoplastic compounds comprises approximately 0.5wt% to the about impact modifier of 20wt%; Randomly approximately 1wt% to the about impact modifier of 20wt%; Randomly approximately 1wt% to the about impact modifier of 12wt%.Said composition comprises the approximately mineral filler of 6wt% to 35wt%, the randomly approximately extremely approximately mineral filler of 25wt% of 6wt%, the approximately extremely approximately mineral filler of 25wt% of 8wt% in certain embodiments.Said composition also comprises the approximately titanium dioxide with silicone or silicon coating of 4wt% to 20wt%, randomly approximately 6wt% to about 16wt% and in some embodiments approximately 8wt% to the about titanium dioxide with silicone or silicon coating of 16wt%.Said composition randomly further comprises the approximately extremely approximately acid of 5wt% of 0.01wt%, randomly approximately extremely approximately 2wt% and the approximately extremely approximately acid of 1wt% of 0.1wt% in 2 some embodiment of 0.05wt%.This thermoplastic compounds comprises approximately 0 to the about aromatic ethenyl copolymer of 25wt%.If exist, in composition, acid should be at least 0.0035: 1 to the weight ratio of filler; Randomly at least 0.005: 1; Randomly at least 0.0075: 1; Randomly at least 0.015: 1; Randomly at least 0.03: 1; Randomly at least 0.06: 1; Randomly at least 0.12: 1; This depends on desirable balancing performance.Said composition also randomly comprises the approximately additive of 0.01wt% to 7wt%.In one embodiment, the molecular weight of polycarbonate is 46000g/mol at least, 48000g/mol at least randomly, and 50000g/mol at least randomly is based on the polystyrene calibration standard.All aforementioned wt% values all are based on the gross weight of composition.

Composition described herein can comprise primary antioxidant or " stablizer " (for example hindered phenol and/or secondary arylamines) and optional secondary oxidation inhibitor (for example phosphoric acid ester and/or thioesters).Suitable oxidation inhibitor additive for example comprises, organophosphite such as tricresyl phosphite (nonyl phenyl) ester, tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester, two (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphites, distearyl pentaerythrityl diphosphite etc.; Alkylation monohydric phenol or polyphenol; The alkylation reaction product of polyphenol and diene, for example four [methylene radical (3,5-di-t-butyl-4-hydroxyl hydrogenated cinnamate)] methane etc.; The butylation reaction product of p-cresol or Dicyclopentadiene (DCPD); The alkylation quinhydrones; Hydroxylation sulfo-phenyl ether; Alkylidene group-bis-phenol; Benzyl compounds; The ester class of β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid and monohydroxy or polyhydroxy-alcohol; The ester class of β-(5-tertiary butyl-4-hydroxy-3-aminomethyl phenyl) propionic acid and monohydroxy or polyhydroxy-alcohol; The ester class of alkylthio or thioaryl compound, for example distearyl thiopropionate, dilauryl thiopropionate, double tridecyl thiodipropionate, octadecyl-3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester, tetramethylolmethane base-four [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester etc.; The acid amides of β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid etc. perhaps comprises the combination of at least a aforementioned antioxidant.Based on the total composition of 100 weight parts, the consumption of antioxidant is normally approximately 0.01 to about 1 weight part, randomly approximately 0.05 to about 0.5 weight part.

Suitable thermo-stabilizer additive for example comprises, organophosphite is tricresyl phosphite phenylester, tricresyl phosphite (2,6-3,5-dimethylphenyl) ester, tricresyl phosphite (list of mixing-and two-nonyl phenyl) ester etc. for example; Phosphonic acid ester such as phenyl-phosphonic acid dimethyl esters etc., phosphoric acid ester such as trimethyl phosphite 99 etc. perhaps comprise the combination of at least a aforementioned hot stablizer.Based on the total composition of 100 weight parts, the consumption of thermo-stabilizer is normally approximately 0.01 to about 5 weight parts, randomly approximately 0.05 to about 0.3 weight part.

Can also use photostabilizer and/or UV-light (UV) absorption agent.Suitable photostabilizer additive for example comprises, benzotriazole such as 2-(2-hydroxy-5-methyl base phenyl) benzotriazole, 2-(2-hydroxyl-uncle's 5-octyl phenyl) benzotriazole and Octabenzone etc. perhaps comprise the combination of at least a aforementioned photostabilizer.Based on the total composition of 100 weight parts, the consumption of photostabilizer is normally approximately 0.01 to about 10 weight parts, randomly approximately 0.1 to about 1 weight part.

Suitable UV absorption agent for example comprises, dihydroxy benaophenonel; Hydroxybenzotriazole; The hydroxy benzo triazine; Cyanoacrylate; Oxanilide; Benzoxazinone; 2-(2H-benzotriazole-2-yl) 4-(1,1,3,3-tetramethyl butyl) phenol (CYASORB ^TM5411); 2-hydroxyl-4-n-octyl oxygen benzophenone (CYASORB ^TM531); 2-[4,6-two (2,4-3,5-dimethylphenyl)-1,3,5-triazines-2-yl]-5-(octyl group oxygen) phenol (CYASORB ^TM1164); 2,2 '-(Isosorbide-5-Nitrae-phenylene) two (4H-3,1-benzoxazine-4-ketone) (CYASORB ^TMUV-3638); 1,3-two [(2-cyano group-3,3-diphenylprop enoyl-) oxygen] 2,2-two [[(2-cyano group-3,3-diphenylprop enoyl-) oxygen] methyl] propane (UVINUL ^TM3030); 2,2 '-(Isosorbide-5-Nitrae-phenylene) two (4H-3,1-benzoxazin-4-ones); 1,3-two [(2-cyano group-3,3-diphenylprop enoyl-) oxygen]-2,2-two [[(2-cyano group-3,3-diphenylprop enoyl-) oxygen] methyl] propane; The inorganic materials of nano-scale is titanium oxide, cerium oxide and zinc oxide for example, is all granularity less than the about material of 100 nanometers; Deng, perhaps comprise the combination of at least a aforementioned UV absorption agent.Based on the total composition of 100 weight parts, the consumption of UV absorption agent is normally approximately 0.1 to about 5 weight parts.

Can also use the additives such as softening agent, lubricant and/or releasing agent.Have very large overlappingly between the material of these types, these materials comprise for example phthalic ester, dioctyl-4 for example, 5-epoxy-hexahydrophthalic acid ester; Three (hot oxygen carbonyl ethyl) isocyanuric acid ester; Tristearoylglycerol; Two or multifunctional aromatic phosphate acid ester, as two (phenylbenzene) phosphoric acid ester of resorcinol tetraphenyldiphosphate (RDP), quinhydrones and two (phenylbenzene) phosphoric acid ester of bisphenol-A; Poly-alpha olefins; Epoxidised soybean oil; Organosilicon comprises silicone oil; Ester, for example fatty acid ester such as alkyl stearyl are as methyl stearate; Stearic acid stearyl, pentaerythritol tetrastearate etc.; The mixture that comprises the hydrophilic of polyethylene glycol polymer, polypropylene glycol polymers and multipolymer thereof and oleophylic nonionic surface active agent and methyl stearate, for example the polyethylene glycol-propylene glycol copolymers in suitable solvent and the mixture of methyl stearate; Wax is as beeswax, montanin wax, paraffin etc.The common consumption of above-mentioned materials is approximately 0.1 to about 20 weight parts, randomly approximately 1 to about 10 weight parts, take the composition total weight of 100 weight parts as benchmark.

Term " static inhibitor " refer to be manufactured into fluoropolymer resin and/or spray to material or goods on to improve haplotype, oligomeric or the polymer-based material of conductivity and whole physicals.The example of haplotype static inhibitor comprises Zerol, Stearic diglyceride, tristearin, ethoxylated amines, primary amine, secondary amine and tertiary amine, ethoxylation alcohols, alkyl-sulphate, alkyl aryl sulfate, alkylphosphonic, alkylamine vitriol, such as stearyl sodium sulfonate, Sodium dodecylbenzene sulfonate etc. of alkylsulfonate, quaternary ammonium salt, Quaternary Ammonium Resin, imidazolidine derivatives, sorbitan ester, glycollic amide, trimethyl-glycine etc. perhaps comprise the combination of at least a aforementioned monomer type static inhibitor.

The polymer type antistatic agent of demonstration comprises some polyesteramide, polyphenylene ether-polyamide (polyetheramides) segmented copolymer, polyether ester amides segmented copolymer, polyether ester or urethane, contains separately polyalkylene glycol moiety such as polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol etc.These polymer type antistatic agents are available commercially, for example, and Pelestat ^TM6321 (Sanyo), Pebax ^TMMH1657 (Atofina) and Irgastat ^TMP18 and P22 (Ciba-Geigy).Other polymer-based material that can be used as static inhibitor is that polymkeric substance such as the polyaniline of person's character conduction (is bought from Panipol EB), polypyrrole and Polythiophene (buy from Bayer and obtain), at high temperature still kept some its intrinsic electroconductibility after melt-processed.In one embodiment, carbon fiber, carbon nanofiber, carbon nanotube, carbon black or aforesaid any combination all can be used for containing the fluoropolymer resin of chemical static inhibitor so that the electrostatic dissipation of composition.Based on the total composition of 100 weight parts, the consumption of static inhibitor is normally approximately 0.1 to about 10 weight parts.

Can also exist toner for example pigment and/or dye additive.Suitable pigment for example comprises, mineral dye is such as metal oxide and mixed metal oxide, such as zinc oxide, titanium dioxide, ferric oxide etc.; Sulfide such as zinc sulphide etc.; Aluminate; Thiosilicic acid salt sodium sulfate (sodium sulfo-silicatessulfates), chromic salt, etc.; Carbon black; Zinc ferrite; Ultramarine blue; Pigment brown 24; Pigment red 101; Pigment Yellow 73 119; Pigment dyestuff is as azo, diazonium, quinoline Azone, perylene, naphthalene tetracarboxylic acid, flavanthrone, isoindolinone, tetrachloroisoindolinone, anthraquinone, anthanthrene diketone, dioxazine, phthalocyanine and azo lake; Pigment blue 60, pigment red 122, pigment red 149, Pigment red 177, pigment red179, Pigment red 202, pigment violet 29, pigment Blue 15, pigment Green 7, pigment yellow 147 and Pigment Yellow 73 150 perhaps comprise the combination of at least a above-mentioned pigment.The consumption of pigment is generally approximately 0.01 to about 10 weight parts, take the composition total weight of 100 weight parts as benchmark.

Suitable dyestuff is generally organic materials and for example comprises, coumarine dye such as tonka bean camphor 460 (blueness), coumarin 6 (green), Nile red etc.; Lanthanide complexes; The hydrocarbon dyestuff of hydrocarbon and replacement; Polycyclic aromatic hydrocarbon dyestuff; Flicker dyestuff Zhu such as oxazole Huo oxadiazole dyestuff; Aryl-or the poly-(C of heteroaryl-replacement _2-8) the alkene dyestuff; Carbonyl cyanine dye; Indanthrene dye; Phthalocyanine pigment; Oxazine dye; The carbonyl styryl dye; The naphthalenetetracarbacidic acidic dyestuff; Porphyrin dye; Two (styryl) biphenyl dyestuff; Acridine dye; Anthraquinone dye; Cyanine dyes; Methine dyes; Arylmethane dyes; Azoic dyestuff; Indigoide colors, thioindigoid dyestuff, diazotizing dyes; Nitro-dye; Quinonimine dye; Aminoketone dye; Tetrazolium dye; Thiazole dye; The perylene dyestuff; Perylene ketone (perinone) dyestuff; 2-benzoxazolyl thiophene (BBOT); Triarylmethane dye; Xanthene dye; The thioxanthene dyestuff; The naphthalimide dyestuff; Lactone colouring matters; Fluorophore, as anti-Stokes shift dyes, it absorbs near-infrared wavelength and launches visible wavelength etc.; Luminescent dye is as 7-amino-4-methylcoumarin; 3-(2 '-benzothiazolyl)-the 7-diethyl amino coumarin; 2-(4-xenyl)-5-(4-tert-butyl-phenyl)-1,3, the 4-oxadiazole; 2,5-two (4-xenyl) ,-oxazoles; 2,2 '-dimethyl-p-quaterphenyl; 2,2-dimethyl-p-terphenyl; 3,5,3 " " 5 " "-tetra-tert-p-quinquephenyls; 2,5-phenylbenzene furans; 2，5-diphenyloxazole; 4,4 '-the phenylbenzene stilbene; 4-dicyano methylene-2-methyl-6-(p-dimethylamino styryl)-4H-pyrans; 1,1 '-diethyl-2,2 '-the carbocyanine iodide; 3,3 '-diethyl-4,4 ', 5,5 '-dibenzo sulfo-three carbocyanine iodide; 7-dimethylamino-1-methyl-4-methoxyl group-8-azepine quinolone-2; 7-dimethylamino-4-methyl quinolone-2; 2-(4-(4-dimethylaminophenyl)-1,3-butadiene base)-3-ethyl benzothiazole perchlorate; 3-diethylamino-7-diethyl imino-Fen oxazole perchlorate; 2-(1-naphthyl)-5-Ben Ji oxazole; 2,2 '-p-phenylene-two (5-Ben Ji oxazole); Rhodamine 700; Rhodamine 800; Pyrene; 1,2-benzophenanthrene (chrysene); Rubrene; Cool; Deng, perhaps comprise the combination of at least a aforementioned dyestuff.The consumption of dyestuff is generally approximately 0.1ppm to about 10ppm, take composition total weight as benchmark.

Addible suitable fire retardant can be the organic compound that comprises phosphorus, bromine and/or chlorine.Non-bromination and non-chlorination phosphonium flame retardant may be preferred for the reason of rules in some applications, for example organophosphate (salt) and contain the organic compound of phosphorus-to-nitrogen bonds.

The exemplary organophosphate of one class is formula (GO) ₃The aromatic phosphate acid ester of P=O, wherein each G is alkyl, cycloalkyl, aryl, alkaryl or aralkyl independently, prerequisite is that at least one G is aromatic group.Two G groups can link together to provide cyclic group, for example, the diphenyl pentaerythritol bisphosphate, it is described in United States Patent (USP) 4154775 by Axelrod.other suitable aromatic phosphate acid ester can for, for example, phenyl two (dodecyl) phosphoric acid ester, phenyl two (neo-pentyl) phosphoric acid ester, phenyl two (3, 5, 5 '-the trimethylammonium hexyl) phosphoric acid ester, ethyl-2-phenyl-phosphate, 2-ethylhexyl two (p-tolyl) phosphoric acid ester, two (2-ethylhexyl) p-tolyl phosphoric acid ester, the trimethylphenyl phosphoric acid ester, two (2-ethylhexyl) phenyl phosphate ester, three (nonyl phenyl) phosphoric acid ester, two (dodecyls) p-tolyl phosphoric acid ester, the dibutyl phenyl phosphate ester, 2-chloroethyl diphenyl phosphoester, p-tolyl two (2, 5, 5 '-the trimethylammonium hexyl) phosphoric acid ester, 2-ethylhexyl diphenyl phosphate, etc..Concrete aromatic phosphate acid ester is that wherein each G is the phosphoric acid ester of aromatic group, for example, and Triphenyl phosphate, lindol, isopropylated triphenyl phosphates etc.

Two or multifunctional aromatics P contained compound be also useful, the compound of following formula for example:

Each G wherein ¹To have 1 to the about hydrocarbon of 30 carbon atoms independently; Each G ²To have 1 to approximately hydrocarbon or the-oxyl of 30 carbon atoms independently; Each X ^aAs defined above; Each X is bromine or chlorine independently; M is 0 to 4, n to be 1 to approximately 30.Suitable two-or the example of multifunctional aromatics P contained compound comprise two (phenylbenzene) phosphoric acid ester of resorcinol tetraphenyldiphosphate (RDP), quinhydrones and two (phenylbenzene) phosphoric acid ester of dihydroxyphenyl propane, their oligopolymer and counterparts of polymkeric substance etc. separately.

The suitable fire-retardant compound example that contains phosphorus-to-nitrogen bonds comprises phosphonitrile muriate, phosphide acid amides, phosphoamide, phosphonic acid amide, phosphinic acid amide, three ('-aziridino) phosphine oxide.

The halo material also can be used as fire retardant, for example halogenated compound and the resin of formula (23):

Wherein R is alkylene, alkylidene or alicyclic connection base, such as methylene radical, ethylidene, propylidene, isopropyl support, isopropylidene, butylidene, isobutyl support, pentamethylene, cyclohexalene, cyclopentylidene etc.; Perhaps oxygen ether, carbonyl, amine or sulfur-bearing connect base, such as sulfide, sulfoxide, sulfone etc.R also can be made of two or more alkylenes or alkylidene key, its by such as aromatics, the group connections such as amino, ether, carbonyl, thioether, sulfoxide, sulfone.

Ar and Ar ' are single-or many carbocyclic aromatic group such as phenylene, biphenylene, inferior terphenyl, naphthylidene etc. independently of one another in formula (23).

Y is organic and inorganic or organometallic group, and (1) halogen for example is as chlorine, bromine, iodine, fluorine; The perhaps ether shown in (2) general formula OE, wherein E is the univalence hydrocarbyl that is similar to X; Perhaps that class univalence hydrocarbyl of (3) R representative; Perhaps (4) other substituting group, such as nitro, cyano group etc., described substituting group is inertia basically, condition is that at least one and optional two halogen atoms are arranged on each fragrant core.

If exist, each X is univalence hydrocarbyl independently, such as alkyl such as methyl, ethyl, propyl group, sec.-propyl, butyl, decyl etc.; Aryl such as phenyl, naphthyl, xenyl, xylyl, tolyl etc.; With aralkyl such as phenmethyl, ethylphenyl etc.; Alicyclic group such as cyclopentyl, cyclohexyl etc.Univalence hydrocarbyl itself can comprise inert substituent.

Each d is 1 maximum value to the number of fragrant nuclear substituted, the replaceable hydrogen that consists of Ar or Ar ' independently; Each e is the maximum value of 0 to R upper replaceable hydrogen number independently.Each a, b and c comprise 0 integer.If b is not 0, a or c are not 0.Otherwise a or c can be 0, but are not 0 simultaneously.When b was 0, aromatic group connected by direct carbon-carbon bond.

Hydroxyl on described aryl Ar and Ar ' and Y substituting group can be on aromatic ring the neighbour, or contraposition changes and this group can be in any possible geometric relationship each other

Be included in the following formula scope is following representational bis-phenol: 2,2-two-(3,5-dichlorophenyl)-propane; Two-(2-chloro-phenyl-)-methane; Two-(2,6-dibromo phenyl)-methane; 1,1-two-(4-iodophenyl)-ethane; 1,2-two-(2,6-dichlorophenyl)-ethane; 1,1-two-(2-chlorine-4-iodine phenyl)-ethane; 1,1-two-(2-chloro-4-aminomethyl phenyl)-ethane; 1,1-two-(3,5-dichlorophenyl)-ethane; 2,2-two-(3-phenyl-4-bromophenyl)-ethane; 2,6-two-(4,6-dichloro naphthyl)-propane; 2,2-two-(2,6-dichlorophenyl)-pentane; 2,2-two-(3,5-dibromo phenyl)-hexane; Two-(4-chloro-phenyl-)-phenylmethane; Two-(3,5-dichlorophenyl)-cyclohexyl-methane; Two-(3-nitro-4-bromophenyl)-methane; Two-(4-hydroxyl-2,6-two chloro-3-p-methoxy-phenyls)-methane; With 2,2-two-(3,5-, two chloro-4-hydroxy phenyls)-propane, 2,2-two-(3-bromo-4-hydroxy phenyl)-propane.What be included in equally above structural formula scope is: 1,3-dichlorobenzene, Isosorbide-5-Nitrae-dibromobenzene, 1,3-, two chloro-4-hydroxybenzenes, and biphenyl such as 2,2 '-DCBP, poly-bromination 1,4-two phenoxy group benzene, 2,4 '-'-dibromobiphenyl and 2,4 '-DCBP and decabromodiphynly oxide etc.

Also available is oligomeric and the poly halogenated aromatic compound, as the Copolycarbonate of dihydroxyphenyl propane and tetrabromo-bisphenol and carbonate precursor such as phosgene.Metal synergistic agent such as weisspiessglanz also can use together with fire retardant.

Can also use inorganic combustion inhibitor, for example C _2-16The salt of alkylsulfonate, such as potassium perfluorobutane sulfonate (Rimar salt), Perfluorooctane sulfonates potassium, perflexane acidfonic tetraethylammonium and sulfobenzide potassium sulfonate etc.; By the salt that the reaction of basic metal for example or alkaline-earth metal (for example lithium, sodium, potassium, magnesium, calcium and barium salt) and mineral acid complexing salt is formed, for example oxo-anions or fluo anion complex compound, the oxo-anions complex compound is the alkali and alkaline earth metal ions salt of carbonic acid for example, such as Na ₂CO ₃, K ₂CO ₃, MgCO ₃, CaCO ₃And BaCO ₃, the fluo anion complex compound is such as Li ₃AlF ₆, BaSiF ₆, KBF ₄, K ₃AlF ₆, KAlF ₄, K ₂SiF ₆And/or Na ₃AlF ₆Deng.

Another kind of available fire retardant is foregoing polysiloxane-polycarbonate copolymer with comprising the polydiorganosiloxane block of repeated structural unit shown in formula (20).

Also can use dripping inhibitor, for example form fibril or do not form the fluoropolymer of fibril, as tetrafluoroethylene (PTFE).Dripping inhibitor can be sealed by rigid copolymer as above such as SAN.The PFFE that is encapsulated in SAN is called as TSAN.The fluoropolymer of sealing can under fluoropolymer exists, for example in aqueous dispersion, make by the polymerization sealed polymer.TSAN can provide significant benefit than PTFE, because TSAN is easier to be distributed in composition.Suitable TSAN for example can comprise the PTFE of about 50wt% and the about SAN of 50wt%, take the gross weight of sealing fluoropolymer as benchmark.SAN for example can comprise the vinylbenzene of about 75wt% and the about vinyl cyanide of 25wt%, take the gross weight of multipolymer as benchmark.As selection, fluoropolymer can some mode and another polymkeric substance such as aromatic polycarbonate resin or SAN be pre-mixed, to form the agglomeration material as dripping inhibitor.Both, any method may be used to make the fluoropolymer of sealing.

When the needs foam, suitable whipping agent for example comprises: the whipping agent of lower boiling halohydrocarbon and those generation carbonic acid gas; Be solid and produce gas such as the whipping agent of nitrogen, carbonic acid gas, ammonia when being heated to above the temperature of its decomposition temperature in room temperature, the metal-salt of Cellmic C 121, Cellmic C 121,4 for example, 4 '-oxygen two (benzol sulfohydrazide), sodium bicarbonate, volatile salt etc., or comprise the combination of at least a above-mentioned whipping agent.

Thermoplastic compounds can prepare by the known ordinary method of prior art, for example in one embodiment as a kind of operating method, at first polycarbonate resin, mineral filler, acid or the acid salt of efflorescence, optional impact modifier, optional aromatic ethenyl copolymer and any other optional components is blended together, randomly with other filler at Henschel ^TMHigh-speed mixer or other suitable mixing tank/stirrer for mixing.Other low shearing method includes but not limited to manual mixing, so also can complete this blending operation.Then blend is dropped into the opening for feed of twin screw extruder via hopper.As selection, one or more components can directly add forcing machine to sneak into composition from opening for feed and/or downstream by the side stuffer.Above-mentioned additive also can become in masterbatch with required polymer resin compounding and add forcing machine.Forcing machine is operating higher than making at the mobile required temperature of composition usually.Make extrudate chilling and granulation in water-bath.The pellet that so makes when cutting off extrudate can be 1/4th inches long or shorter length on demand.Such pellet can be used for molding, shaping or moulding subsequently.

The shaping, moulding or the moulded parts that comprise described thermoplastic compounds also are provided.Can be with described thermoplastic compounds by the whole bag of tricks such as injection moulding, extrude, rotational molding, blowing and thermoforming be molded as useful moulded products, thereby form goods such as computer and business machine shell, shell, palmtronic shell such as phone housing as watch-dog, series of cells, electric power connector, and illuminating equipment, ornament, home appliances, roof, greenhouse, glass sunlight house, swimming pool enclose the element of grid, electronic equipment casing and sign etc.In addition, polycarbonate compositions also can be used for application such as the wall in trolley part (comprising panel and interior trim, turbulence generator, luggage-boot lid, body panels (body panel)) and tourist automobile and structure unit.Further explain said composition by following indefiniteness embodiment, it is prepared by the listed component of table 1.

Table 1

Prepare sample composition according to the amount in table 2 with the material in table 1 and screen different titanium dioxide.All amounts are all weight percentage.All samples has the component (100 weight parts altogether) of same amount, then dissimilar and titanium dioxide quantity is added in these compositions.The first sample is control sample.In each embodiment, adopt Werner ﹠amp; Pfleider ^TMThe 25mm twin screw extruder approximately 280 ℃ the nominal melt temperature, approximately 0.7 bar vacuum tightness and approximately make sample by melt extruding under the 450rpm condition.With the extrudate granulation and at approximately under 100 ℃ dry approximately 2 hours.In order to make test sample, the pellet of drying is carried out injection moulding with 110 tons of injection moulding machines when the nominal melt temperature of 300 ℃, wherein melt temperature is slightly high approximately 5～10 ℃.

Table 2

Component	Unit	Contrast	Embodiment A-1	Embodiment A-2	Embodiment A-3	Embodiment A-4	Embodiment A-5	Embodiment A-6	Embodiment A-7	Embodiment A-8
											The PC blend	％	77.13	77.13	77.13	77.13	77.13	77.13	77.13	77.13	77.13
SAN	％	9.5	9.5	9.5	9.5	9.5	9.5	9.5	9.5	9.5
											MBS	％	4.4	4.4	4.4	4.4	4.4	4.4	4.4	4.4	4.4
Filler	％	8	8	8	8	8	8	8	8	8
											Acid	％	0.12	0.12	0.12	0.12	0.12	0.12	0.12	0.12	0.12
TiO 2-1	％	0	1.0	2.5	0	0	0	0	0	0
											TiO 2-2	％	0	0	0	1.0	2.5	0	0	0	0
TiO 2-3	％	0	0	0	0	0	1.0	2.5	0	0
											TiO 2-4	％	0	0	0	0	0	0	0	1.0	2.5
Additive *	％	0.85	0.85	0.85	0.85	0.85	0.85	0.85	0.85	0.85
											Physical properties	Unit
The Izod notched Izod impact strength, 23 ℃	kJ/m 2	40.0	40.4	42.6	34.4	16.0	34.9	29.1	36.1	35.5
											Tensile modulus	MPa	3100	3142	3175	3137	3175	3138	3176	3156	3199
The MW retentivity	％	100	99	97	99	98	98	96	95	99

^*Additive comprises stabilizer package, described stabilizer package comprises the tetramethylolmethane four (3-lauryl thiopropionate) of the antioxidant of 0.25wt%, the tricresyl phosphite of 0.1wt% (two-tert-butyl-phenyl) ester, 0.25wt% and the releasing agent (based on the composition that comprises stabilizer package of 100 weight parts) of 0.25wt%, and this also adds in composition.

As can be seen from Table 2, have 4 kinds of dissimilar TiO ₂The different in kind of sample in control sample.The shock resistance of embodiment A-3 and A-4 significantly reduces, and comprises the TiO of coating ₂Embodiment A-1, A-2, A-5, A-6, A-7 and A-8 unexpectedly show: character or do not significantly improve or reduce, perhaps slightly improve on shock resistance.The decline of shock resistance is expected, and this is because TiO ₂Usually do not improve mechanical property.Especially unexpectedly the TiO that applies ₂Or keep or the raising performance, this depends on the TiO of concrete use ₂

Utilize the material in table 1 to prepare other sample, and method as previously mentioned.Mode with increment is added TiO ₂-1.Fill a prescription and the results are shown in following table 3.All amounts in table 3 are weight percentage, unless illustrate in addition.

Table 3

Component	Unit	Embodiment B-1	Embodiment B-2	Embodiment B-3	Embodiment B-4	Embodiment B-5
							PC-1	％	53.36	51.76	48.56	45.76	39.76
PC-2	％	13.35	12.95	12.15	15.25	13.25
							SAN	％	9.5	9.5	9.5	9.5	9.5
MBS	％	4.4	4.4	4.4	4.4	4.4
							Filler	％	18	18	18	16	16
Acid	％	0.54	0.54	0.54	0.24	0.24
							TiO 2-1	％	0	2.0	6.0	8.0	16.0
Additive *	％	0.85	0.85	0.85	0.85	0.85
							Physical properties	Unit
The Izod notched Izod impact strength, 23 ℃	kJ/m 2	9.9	10.0	13.8	15.7	18.3
							Corrugated plate shock strength ductility, 23 ℃	％	100	100	100	100	100
Corrugated plate shock strength ductility, 0 ℃	％	100	0	0	100	0
							Tensile modulus	MPa	4346	4547	4772	4544	5031
Dimension card B/50	℃	139.1	139.3	139.1	139.4	138.6
							MVR，260℃5kg	cm 3/10 min	5.2	4.6	5.5	6.0	5.8
PC MW retentivity	％	97	99	98	98	98

^*Additive comprises stabilizer package, described stabilizer package comprises the tetramethylolmethane four (3-lauryl thiopropionate) of the antioxidant of 0.25wt%, the tricresyl phosphite of 0.1wt% (two-tert-butyl-phenyl) ester, 0.25wt% and the releasing agent (based on the composition that comprises stabilizer package of 100 weight parts) of 0.25wt%, and this also adds in composition.

Embodiment B-1, B-2 and B-3 show increases TiO ₂Effect.Izod notched Izod impact strength and tensile modulus are all with TiO ₂Increase and significantly increase, yet Wei Ka and MVR do not show noticeable change.Ductility in the time of can not keeping 0 ℃ during 18% talcum level, but the TiO of 16% talcum and 8% ₂The time (Embodiment B-4, it is also than Embodiment B-2%TiO more than 3 ₂) ductility when obtaining 0 ℃, and higher Izod notched Izod impact strength and than high workability (MVR).Comparative Examples B-4 and B-2 show higher level TiO ₂When slightly hanging down the talcum carrying capacity, all these physical propertiess are improved.In addition, Comparative Examples B-4 and B-1 show: although Embodiment B-4 have the TiO of less talc filler and more coating ₂, yet but rigidity exists little increase Izod notched Izod impact strength significantly to increase, and mobility (MVR) increases.This is unexpected, because be 18% to compare with the total filler level of Embodiment B-1, and the total filler level (talcum+TiO of Embodiment B-4 ₂) be 24%.Obtained excellent performance balance when higher level, Embodiment B-5 for example, it has very high tensile modulus (rigidity) and high Izod notched Izod impact strength and excellent fluidity.

Utilize the material in table 1 to prepare other sample, and method as mentioned above.These other samples have been studied the TiO that adds two kinds of different coatings with different levels ₂Sample (TiO ₂-1 and TiO ₂-3) and the talcum of different levels.In certain embodiments, also PMHS is added in described composition and come research effect.The composition of sample is shown in following table 4, and test-results is listed in the table below 5.

Claims (15)

1. thermoplastic resin composition, the gross weight by composition comprises:

The aromatic polycarbonate of 30wt%～89.5wt%, the molecular weight of wherein said polycarbonate is 50000g/mol at least, based on the polystyrene calibration standard;

The impact modifier of 0.5wt%～20wt%;

The aromatic ethenyl copolymer of 0wt%～25wt%;

The talcum of 6wt%～35wt%;

Acid or acid salt; And

The titanium dioxide of 4wt%～20wt%, wherein said titanium dioxide-coated has silicone or siloxanes, and the gross weight of wherein said composition is 100wt%.

2. the thermoplastic compounds of claim 1, wherein said acid or acid salt comprise phosphorus.

3. the thermoplastic compounds of claim 1, wherein said acid or acid salt with at least 0.0035: 1 acid to filler weight than existing.

4. the thermoplastic compounds of claim 1, wherein said impact modifier comprises ABS, MBS, AES, ASA, MABS, polycarbonate-polysiloxane copolymer, and combination.

5. the thermoplastic compounds of claim 1, wherein said aromatic ethenyl copolymer comprises SAN.

6. the thermoplastic compounds of claim 1, the size-grade distribution D50 of wherein said talcum is 3 microns or less.

7. the thermoplastic compounds of claim 1, wherein said composition comprises the titanium dioxide of 6wt%～16wt%.

8. the thermoplastic compounds of claim 4, wherein ABS is body ABS.

9. the thermoplastic resin composition of claim 1, wherein said composition comprises the aromatic polycarbonate of 50wt%～85wt%, the impact modifier of 1wt%～12wt%, the talcum of 8wt%～25wt%, the titanium dioxide of 6wt%～16wt%, and the aromatic ethenyl copolymer of optional 2wt%～15wt%, the gross weight of composition is 100wt%.

10. the goods that comprise the thermoplastic compounds of claim 1.

11. a thermoplastic compounds, by the gross weight of composition, it is composed as follows:

The aromatic polycarbonate of 50wt%～85wt%, the molecular weight of wherein said polycarbonate is 50000g/mol at least, based on the polystyrene calibration standard;

The impact modifier of 1wt%～20wt%;

The aromatic ethenyl copolymer of 2wt%～25wt%;

The talcum of 8wt%～25wt%;

The acid of 0.01wt%～5wt% or acid salt;

The titanium dioxide of 4wt%～20wt%, wherein this titanium dioxide-coated has silicone or siloxanes; And

The additive of 0.01wt%～7wt%, wherein said additive comprises the combination of filler, dripping inhibitor, thermo-stabilizer, photostabilizer, antioxidant, softening agent, static inhibitor, releasing agent, lubricant, tinting material or two or more aforementioned substances, and the gross weight of composition is 100wt%.

12. the thermoplastic compounds of claim 11, wherein said composition comprises the titanium dioxide of 6wt%～16wt%.

13. the thermoplastic compounds of claim 11, wherein said photostabilizer are the UV absorption agent.

14. the thermoplastic compounds of claim 11, wherein said tinting material is selected from pigment and dyestuff.

15. comprise the goods of the thermoplastic compounds of claim 11.